5th International Zeolite Membrane Meeting, May 23rd -26th 2010

Preparation and Characterization of Alumina-Silica Membranes

Berna Topuz, Muhsin iftiolu
Izmir Institute of Technology, Chemical Engineering Department, Turkey
(bernatopuz@iyte.edu.tr)
Mullite formation at relatively low temperatures can be observed with controlled structures and
surface chemistry due to the molecular scale mixing of alumina and silica in sol-gel processing. Differences
in hydrolysis rate of Al(III) and Si(IV) alkoxides may however result in some segregation which may prevent
the formation of chemically homogeneous mullite oxide network. A variety of crystallization reactions from
chemically synthesised precursors results in the formation of mullite ceramics with high chemical purity in
the temperature range of 850oC to 1350oC [1-2].
The development of mullite membrane with microporous network would have particular importance
due to its high thermal stability. In this study, sol-gel derived alumina-silica membranes were prepared by a
simple method involving the mixing of stable polymeric alumina sol with polymeric silica sol in Al2O3:SiO2
ratio of 3:2 (mullite composition) in order to investigate the mullite crystallization upon heat treatment.
The formation of mullite upon heat treatment of unsupported membrane powders at 775oC was
observed by the presence of peaks at 2 values of ~16o, 26o, 35o and 45o, etc as shown in Figure 1. These
peaks correspond to stoichiometric mullite, 3Al2O3.2SiO2 (JCPDS, card file 15-776). This XRD pattern
clearly demonstrates that pure mullite phase could be obtained by using stable polymeric alumina and silica
sols at around 775oC which is the lowest reported mullite formation temperature known by the authors. There
is no indication for the formation of the spinel phase (sharp 2 peak at 43o) indicating the formation of a very
homogeneous structure because of a high degree of atomic mixing [3].
800
o
800 C
15-776
700
o
775 C
o
600
850 C

800
600
400

800oC
775oC

200

800 C
775 C

500

25

26

27

Intensity (Arb.Units)

400
300

850oC

200

800oC
15-776

100

775oC

0
10

30

50
2
theta
2 (deg.)
o

70

Figure 1. XRD patterns of unsupported mullite membranes heat treated at different temperatures.
The presence of sharp mullite peaks above 775oC which were the strongest peaks at 850oC indicates
a high level of mullite crystallinity and the variation of XRD derived mullite crystallite size with temperature
can be seen in Figure 2. The small variation in crystallite size with the heat treatment temperature indicated
the stability of microstructure with insignificant coarsening in this temperature range. This relatively low
mullite transformation temperature could be attributed to the highly reactive amorphous silica precursor used
in the mullite formulation besides the high specific surface of nanosized boehmite species present in the
precursor polymeric alumina sol. The extended scale of 2 values in the 25-27o range is also given in the
insert in Figure 1 where a clear splitting of the peak at 26o is known as a direct indication of the orthorhombic
mullite formation [3].

5th International Zeolite Membrane Meeting, May 23rd -26th 2010

45

26o
30o

40
Crystallite Size (nm)

33o

35
30
25
20
15
760

780

800

820

840

860

Temperature ( C)
Figure 2. Crystallite size variation with heat treatment temperature.

The mixing of freshly prepared polymeric silica and polymeric alumina sols in mullite compositions (3:2) led
to the crystallization of mullite upon heat treatment at 775oC. This very low transformation temperature is
most likely related with the final homogeneously mixed stable oxide network with very fine microstructure.
XRD patterns of unsupported mullite membrane powders prepared by mixing of aged sols are given
in Figure 3 (a). The shift in mullite transformation temperature to 875oC might be due to the increase in sol
particle sizes.
10

(a)

(b)
0

Intensity (Arb.Units)

800

Shrinkage (%)

900 C

1000

875 C

600

850 C

400
200

-10

270 oC

970 oC
945 oC

194 oC

-20

-3

-30

-5

153 oC

0
0

20

40
2 2
theta
(deg.)

60

-2

-4

800 C

3Al2O3.2SiO

-1

320 oC

80

-6

-40
0

200

400

600
800
o
Temperature ( C)

1000

1200

Figure 3. (a) XRD patterns (b) shrinkage and shrinkage rate curves of unsupported mullite membranes
The corresponding dimensional change and shrinkage rate curves of unsupported mullite membrane powder
pellets are given in Figure 3 (b). Rapid shrinkage at 150oC may be due to the fast removal of the solvent. The
total shrinkage of about 25% below 400oC could be ascribed to the removal of organics and the
polymerization of the inorganic networks. XRD mullite transformation temperature of membranes prepared
from aged sol closely correlated the shrinkage at 945oC. Holding time difference for both experiments may
cause the temperature difference for mullite formation. The final linear shrinkage was 35%.
The mixing of freshly prepared polymeric silica and alumina sols in mullite compositions led to the
crystallization of mullite upon heat treatment at 775oC. This very low transformation temperature is most
likely related with the final homogeneously mixed stable oxide network with very fine microstructure. The
preparation of thin defect free microporous alumina-silica membrane layers necessitates the optimization of
process parameters controlling the dipping/drying/heat treatment steps as well as the sol concentration
closely.

References
[1] F. Griggio, E. Bernardo, P. Colombo, G.L. Messing, J. Am. Ceram. Soc. (2008), 91 (8), 2529-2533.
[2] S. Sunderesan, .A. Aksay, J. Am. Ceram. Soc. (1991), 74 (10), 2388-2392.
[3] P. Kansal, R. A. Laine, J. Am. Ceram. Soc. (1997), 80 (10), 2597-2606.

1200

Shrinkage rate (1/ C)

1400