Powder Technology 155 (2005) 187 192 www.elsevier.

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Study on the formation process of Al2O3 TiO2 composite powders

Shiquan Liu *, Wenhong Tao, Jia Li, Zhongxi Yang, Futian Liu
School of Materials Science and Engineering, Jinan University, Jinan, Shandong 250022, China Received 24 August 2004; received in revised form 23 March 2005; accepted 18 May 2005 Available online 14 July 2005

Abstract Fine particles of anatase were suspended in solutions of ammonium alum with Al2O3/TiO2 molar ratios from 0.1:1 to 7:1. By spray drying the suspensions and calcining the spray-dried powders, Al2O3 TiO2 composite particles were obtained. The results show that after the spray drying, coatings of ammomium alum are formed on the surface of the anatase particles, leading to composite precursor powders (CCPs) with larger particle sizes. Upon calcining the CCPs, ammomium alum pyrolyzes to amorphous Al2O3 and anatase transforms into rutile. Both are mainly responsible for the observed particle size reductions as well as the densification of each composite particle. The in-situ formed aAl2O3 and rutile may have higher reactivities, forming aluminum titanate at 1150 -C, about 130 -C lower than the theoretical temperature for the formation of Al2TiO5 by solid reaction. The reaction between a-Al2O3 and rutile starts from the interface between the anatase and the alum coating and mainly takes place in the single particles formed by spray drying. The molar ratio of Al2O3 to TiO2 influences the final crystalline phases in the composite powders, but not stoichiometrically. D 2005 Elsevier B.V. All rights reserved.
Keywords: Al2O3 TiO2 composite particle; Aluminum titanate; Spray dyring; Calcination; Crystalline phase

1. Introduction Al2O3 ceramics have been widely used in many fields because of their good mechanical properties, such as high hardness and super abrasion resistance [1,2]. Recently, researchers have tried to improve their performance through additions of other oxides [3 6]. Xiao and his coworkers found that protective coatings on metals, which were prepared from Al2O3 TiO2 composite powders by flamespraying, have much better abrasion resistance than those consisting of pure Al2O3 powders [6]. Wunderlich et al. pointed out that nano-hybrid Al2O3 TiO2 might be applied as catalysts [7]. In addition, ceramics made from Al2O3 TiO2 composite powders show attractive perspectives. Aluminum titanate ceramic is a good example. Owing to its excellent thermal expansion behavior [8 10], it can be used as thermal resistant materials, such as catalyst carriers for purification of fume produced by cars, as containers and tubes for storing or conveying high temperature steel liquid and as protective tube for thermal couples, etc.
* Corresponding author. Tel.: +86 531 2201692; fax: +86 531 7974453. E-mail address: vctrliu@hotmail.com (S. Liu). 0032-5910/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.powtec.2005.05.048

Traditionally, Al2O3 and TiO2 are ball-milled to form composite powder mixtures for the subsequent shaping and sintering process [10]. Other authors have tried new methods such as wet chemical synthesis and high temperature oxidation [7,11,12]. We use spray drying, an industrial technology, to form composite precursor powders (CPPs) of ammonium alum and titania. After calcining the precursor powders, Al2O3 TiO2 composite particles with different crystalline phases are obtained. The most obvious character of the spray drying is that the as-prepared powders are uniformly spherical, which is beneficial to the following conveying and shaping procedure in the manufacturing of ceramic products. In addition, the spray drying introduces less impurity and saves time and energy compared to the traditional ball-milling. We also find that upon calcination the in-situ formed components inside the CPPs show higher chemical reactivities. 2. Experimental Fine anatase powder produced by the sulfate process (Yuxing Chemical Industrial Factory, Jinan) was suspended

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Table 1 Designed compositions of Al2O3 TiO2 composite powders Sample no. Al2O3/TiO2 molar ratio AT1 0.1:1 AT2 0.6:1 AT3 1:1 AT4 1.4:1 AT5 7:1

3. Results and discussion 3.1. Formation of the composite precursor powders (CPPs) upon spray drying Most of the particles prepared by the spray drying are dispersed and spherical (Fig. 1a). A comparison among the mean particle sizes (d 50) of the original anatase and the spray-dried powder shows an increase of d 50 from 4.48 to 17.24 Am, indicating a significant increment of the particle size. Taking AT3 as an example, Figs. 2a and b depict the histograms of particle size distribution of the original anatase powder and the spray-dried powder. As compared with the columns in Fig. 2a, the heights of the first eight columns in Fig. 2b decrease in contrast with increases of the height of the subsequent columns, suggesting that after the spray drying, larger particles are formed. It can also be seen that after the spray drying, the mode shifts to a larger particle size value (Fig. 2b). Meanwhile, the particle size distribution becomes broader, indicated by new columns in the size fractions above 53.5 Am. According to the mechanism of spray drying [6], ammomium alum coating is supposed to be formed on the surface of TiO2 particles. Moreover, EDS analysis (Fig. 1b) reveals that these particles, bigger or smaller in size, all contain elements of O, Al, S and Ti, indicating that spray drying the suspension with anatase powder in the alum solution successfully leads to the formation of composite powder consisting of TiO2 and ammomium alum. TGA analyses reveal that upon heating, the weight losses of the CPPs depend on the A/T ratios (Fig. 3). The larger the A/T ratio is, the more the weight loss is observed. Since the weight loss is mainly due to the thermal decomposition of alum in the CCP, this correlation between the weight losses and the A/T ratios indicates that thicker alum coatings are formed on the surface of anatase in the case of higher A/T

in the solutions of ammonium alum (Dagang Yizhong Chemical Industrial Factory, Tianjing). The molar ratios of Al2O3 to TiO2 (A/T ratio) were changed from 0.1:1 to 7:1 (see Table 1). Spray drying was performed on a QP-3 spray-drier (Research Institute of Chemical Industry, Beijing). The conditions for the spray drying were as follows: pressure of the atomizing air, 0.1 0.2 MPa; flow of feeding, 30 ml/min; temperatures at the inlet and outlet of the spray-drier, 200 T 10 -C and 100 T 10 -C, respectively. Powders collected from the spray-drier were calcined in an electrical furnace with a temperature precision of T 5 -C. The temperatures were set at 700, 864, 1150 and 1368 -C, respectively, with a heating rate of 10 -C/min. The calcined samples were cooled in air directly from high temperatures. X-ray diffractograms (XRD) were recorded on a D/maxrA diffractometer (Rigaku, Japan) to identify the crystalline phase in the calcined samples. A S-2500 Scanning Electron Microscope (SEM) (Hitachi, Japan) equipped with an Energy Dispersive Spectrum (EDS) analyzer (Oxford Co., Britain) was used to analyze the morphology and composition of the powders. The measurements of the powder particle size and its distribution were performed on a FAM Laser Particle Diameter Analyzer (Pike Instrument Co., Shanghai). Histograms of the particle size distribution (PSD) based on the mass frequency were drawn according to the original data. Modes, representing the values that occur most frequently in the distributions, were labeled on the histograms.

~200m

cps

S 15

10 Al O 5

Ti 0 1 2 3 4 5 Energy (keV)

(a)

(b)

Fig. 1. SEM graph (a) and EDS (b) of the composite precursor powder.

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21

mode

0 21

mode

particles by mass

0 21

mode

Frequency,

0 21

mode

0 21

e
mode

0 21

mode

0.5-1.9

1.9-2.4 2.4-3.0 3.0-3.8 3.8-4.8 4.8-6.2 6.2-7.9 7.9-10.1

10.1-13 13-16.7 16.7-21.6 21.16-28.1

Particle Size (m)

Fig. 2. Histograms of the particle size distribution of the CCP and the calcined samples of AT3.

ratios. However, the correlation is not linear, because the calculation of the weight loss of the CCP takes the mass of inner anatase plus the alum coating as a whole, while the former does not lose any weight except the adsorbed water upon heating. 3.2. Reactions in the composite precursor powders (CPPs) upon calcination After being spray-dried, the CCP powders were first calcined at 700 -C, 864 -C and 1150 -C for 2 h,

28.1-37.6 37.6-53.5 53.5-87.1 87.1-1859

respectively. The results of the particle size analysis for the calcined samples of AT3 are also depicted as histograms in Fig. 2. Comparing Fig. 2c e with Fig. 2b, we can see that the modes of the calcined samples are shifting to smaller size values, indicating that the powder particles are becoming smaller upon increasing temperatures. Meanwhile, the PSDs are narrowing. The d 50 values show decreases from 17.24 for CCP to 15.12Y12.02Y7.03 Am after calcinations. SEM observation reveals that most particles in the sample calcined at 1150 -C for 2 h are still spherical (Fig. 4a). However, when the spry-dried powder was calcined at 1368 -C for 20 min, the histogram of PSD shows a significant shift to the large size fractions, suggesting a sharp increase of the particle size. The d 50 value is increased up to 26.07 Am, even larger than that for the spray-dried powder. SEM observation reveals that particles in this case are not spherical at all (Fig. 4b). From the DTA curve of the spray-dried ammomium alum powder (Fig. 5a), it can be seen that weight losses mainly take place below 800 -C, no obvious weight losses have been observed when the temperature is higher than 1000 -C, suggesting that the pyrolysis of ammonium alum is completed. That is to say, ammonium alum in CCPs must have pyrolyzed to Al2O3. Similar results are obtained for the CCPs of AT3 (Fig. 5b). Meanwhile, as it will be illustrated later by the XRD results, some anatase has transformed into rutile in the same temperature region. since rutile is more densely compacted than anatase, the phase transformation can result in a negative volume change [13]. Therefore, it is supposed that the decreases in the particle size under 900 -C are mainly due to the pyrolysis of ammomium alum on the surface of the anatase particles and the volume reduction caused by the anatase-to-rutile transformation. At 1150 -C, densification which occurs inside each composite particle should be mainly responsible for the particle size reduction. At 1368 -C, possibly the inter-particle solid

Fig. 3. Weight losses versus A/T ratios.

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Fig. 4. SEM graphs of the samples calcined at (a) 1150 -C and (b) 1368 -C.

reactions and sintering effect finally lead to the nonspherical morphology and the size increase of the composite particles. Fig. 6 shows the XRD patterns of the calcined AT3 powders. When the spray-dried powder is calcined at 700 -C, only the anatase phase is detected (Fig. 6a). Upon raising the temperature to 864 -C, part of the anatase transforms into rutile (Fig. 6b). This temperature is significantly lower than that for the pure anatase-to-rutile transformation [14,15]. This difference might be caused by the composite effect of the two components in the CCP, especially on the interface between the anatase and the alum coating. It has been found that the incorporation of Al2O3 into anatase can accelerate the anatase-to-rutile transformation [16,17]. The reason is that Al3+ ions, with a valence lower than Ti4+, can create oxygen vacancies due to the necessity of charge balance, reducing the energy barrier for the rearrangement of the Ti O octahedra. Also this composite effect may be responsible for the difference between the thermal decomposition behaviors of a spraydried alum and the CCP. In our previous study [18], the spray-dried ammomium alum powders were subsequently pyrolyzed to crystalline Al2(SO4)3 and g- or u-Al2O3 in a temperature region of 900 -C. However, for the CCP, as indicated by the TGA result, the pyrolysis of ammonium alum is completed under 864 -C. However, no similar crystalline phases are detected, indicating that Al2O3 is in an amorphous state. With the temperature rising to 1150 -C, rutile is still the main crystalline phase, but aluminum titanate (Al2O3ITiO2) is detected along with a-Al2O3 (Fig. 6c) This temperature is about 130 -C lower than the theoretical temperature for the formation of Al2TiO5 through traditional solid reaction between a-Al2O3 and rutile [10,19]. This might be due to the higher reactivities of the rutile and a-Al2O3 formed insitu upon heating. Since the particles are still highly dispersed (Fig. 4a), it is reasonable to believe that the formation of Al2O3ITiO2 mainly takes place in every single particle formed by the spray drying.

From Table 2, it can be seen that at a same calcining temperature below 1150 -C, although the CCPs have different A/T ratios, the crystalline phases in all calcined

Fig. 5. DTA-TG curves for (a) CCp of AT3, (b) spray-dried alum, (c) annatase.

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Fig. 6. XRD patterns for the sample of AT3 calcined at : (a) 700 -C, 2 hr; (b) 864 -C, 2 hr; (c) 1150 -C, 2 hr; (d) 1368 -C, 20 min; (e) 1368 -C, 2 hr.

samples are the same as those in AT3. However, when the temperature is raised to 1368 -C, the reactions are dominated by the formation of Al2O3ITiO2 as the main crystalline phase at the loss of a-Al2O3 and rutile. The final phases are dependent on the A/T ratios, but not stoichiometrically. In the samples with A/T ratios smaller than 1 (such as AT1 and AT2), a-Al2O3 totally disappears, rutile, supposed as an unreacted component, still exists. It is not difficult to understand that rutile co-exists with Al2O3ITiO2 in these cases, because Al2O3 is relatively inadequate for the formation of Al2O3ITiO2. But in AT3 with an A/T ratio of 1:1, rutile is also detected (Fig. 6d). Even in the cases of AT4 and AT5, whose A/T ratios are 1.4 and 7, respectively, rutile is still found along with unreacted a-Al2O3. Comparing the DTA curves in Fig. 6b and c, we can see that each of them shows an endothermal peak at exactly the same temperature, 1367.9 -C, indicative of the normal anatase-to-rutile transformation. This proves that the inner part of the anatase particles is still undergoing phase transformation, although aluminum titanate (Al2O3ITiO2) has been identified to be formed at 1150 -C. It evidences that the formation of Al2O3ITiO2 starts from the interface between the anantase and the alum coatings inside the CCPs. Then the completeness of the formation of Al2O3ITiO2 in each
Table 2 Crystalline phases in the calcined samples Sample no. Calcining temperature/-C 700 864 1150 AT1 Anatase Anatase Rutile Rutile Al2O3ITiO2 a-Al2O3 Al2O3ITiO2 Rutile

single particle relies on the solid diffusion and solid reaction. Therefore, the thickness of the coating plays an important role in the process of the formation of Al2O3ITiO2. Increasing the A/T ratio results in a thicker surface coating of alum on the surface of anatase. Then the transformed rutile in the center part of a single CPP particle is difficult to diffuse to the surface to react with a-Al2O3. Consequently, rutile is still detected although it is s toichiometrically inadequate for the formation of Al2O3ITiO2. This result does not change when the soaking time is prolonged from 20 min to 2 h at this temperature (Fig. 6e).

4. Conclusions 1. The spray-dried composite precursor powder has a core shell structure with coatings of ammonium alum on the surface of anatase particles. The thickness of the alum coating increases with the increase of the Al2O3/TiO2 ratio. 2. Upon calcination of the spray-dried composite precursor powder, pyrolysis of ammomium alum and the anatase to rutile transformation as well as the densification of each composite particle result in the particle size reductions.

AT2 Anatase Anatase Rutile Rutile Al2O3ITiO2 a-Al2O3 Al2O3ITiO2, Rutile

AT3 Anatase Anatase Rutile Rutile Al2O3ITiO2 a-Al2O3 Al2O3ITiO2 Rutile

AT4 Anatase Anatase Rutile Rutile Al2O3ITiO2 a-Al2O3 Al2O3ITiO2 Rutile a-Al2O3

AT5 Anatase Anatase Rutile Rutile Al2O3ITiO2 a-Al2O3 Al2O3ITiO2 Rutile a-Al2O3

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3. During the calcination, ammonium alum pyrolyzes to Al2O3 and anatase transforms into rutile. Al2O3ITiO2 forms at 1150 -C. The reaction between Al2O3 and rutile mainly takes place in every single particle formed through spray drying and starts from the interface. 4. The molar ratio of Al2O3 to TiO2 does not influence the crystalline phases stoichiometrically in the final composite Al2O3 TiO2 powders.

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