Materials Science and Engineering A332 (2002) 91 – 96

www.elsevier.com/locate/msea

Study of sol–gel processing for fabrication of low density alumina

microspheres
Nursel Dilsiz a,*, Güneri Akovalı b
a
Engineering De6elopment Group, PO Box 30, Roketsan, 06780 Elmadag, Ankara, Turkey
b
Departments of Chemistry and Polymer Science and Technology, Middle East Technical Uni6ersity, 06531 Ankara, Turkey

Received 23 April 2001; received in revised form 22 June 2001

Abstract

A sol–gel process for producing microspheres of low density alumina has been developed. A Dispal alumina sol and aluminum
monohydrate were used as starting materials. Microspheres with spherical shape and controllable size have been produced by
using a drop generation technique. The technique consists of producing a continuous stream of uniform droplets of alumina sol
and then converting the drops into a rigid form by exposing them to an ammonium hydroxide gelation medium. By using this
technique, alumina spheres with surface area 351 m2 g − 1 and pore size 10.7 A° have been prepared. © 2002 Elsevier Science B.V.
All rights reserved.

Keywords: Sol– gel processing; Microspheres; Low density alumina

1. Introduction This paper describes the preparation of alumina micro-

spheres by sol gel process. Sol preparation, drop forma-
Sol –gel processes were developed during the mid- tion, gelation, washing, drying and sintering are
1960s for the preparation of ceramic nuclear fuel [1–4]. discussed as well as a process for making large micro-
During recent years, sol gel technology has become spheres (500 –1500 mm) by variation of stream of alu-
attractive for the applications outside of the nuclear mina sol.
fuel industry and has been devoted to preparing for The process of making alumina involves four basic
metallic oxides generally [5 – 8]. The prime requirement steps [10 –12].
of sol gel process is that the oxide component should be
capable of forming a concentrated colloidal sol which 1.1. Hydrolysis of aluminum alkoxides
may be gelled satisfactorily. The sol – gel process con-
sists of forming a concentrated colloidal sol of the
metallic oxides or hydroxides and converting this sol to Al(OR)3 + H2O“ AlOOH + 3ROH
a semi rigid gel. The shape and size of the final oxide
product is determined at the gelation stage, which is Al(OR)3 + 3H2O“ Al(OH)3 + 3ROH
therefore crucial to the whole process.
Alumina is well known for its use as adsorbents, Aluminum alkoxide is hydrolyzed by water, produc-
catalyst and drying agents. Their high surface area and ing aluminum mono- or tri-hydroxides [9]. In both
porosity make microspheres attractive as catalytic sub- cases X-ray of the initial reaction products are not
strates and filters. Their reactive surface permits chemi- different. Poorly crystallized boehmite (‘pseudoboeh-
cal modification and the pores can also be filled with mite’) develops after a few hours of aging the precipi-
polymers to produce strong light-weight composites [9]. tate. Boehmite is the only phase occurring if the
temperature exceeds 350 K during hydrolysis reaction
* Corresponding author. or during aging of an initially amorphous precipitate
E-mail address: [email protected] (N. Dilsiz). [13].

0921-5093/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 1 ) 0 1 7 2 6 - 9
92 N. Dilsiz, G. Ako6alı / Materials Science and Engineering A332 (2002) 91–96

When the aluminum alkoxides are hydrolyzed with 1.4. Pyrolysis to alumina
hot water a stable, crystalline monohydroxide forms.
However, when hydrolysis is performed with cold water After a gel has been obtained in the dry state, it must
the resultant monohydroxide is largely amorphous and be treated further to remove solvent from microspheres.
converted to the trihydroxide, bayerite Al(OH)3. Only Depending upon the nature of the gel and the condi-
the monohydroxide can be peptized to a clear sol [14]. tions of its formation, any of the following reactions
occur during pyrolysis: (1) desorption of absorbed sol-
1.2. Peptization of the hydroxide to a clear sol vent from the walls of micropores; (2) dehydration; (3)
formation of micropores; (4) collapse of micropores; (5)
Peptization is the stabilization of a colloidal sol by densification.
the adsorption of potential determining ions on the In the present study, alumina sol and aluminum
particle surface of the gel. Peptization requires the monohydrate were used as starting materials. The spe-
introduction of a critical amount of certain acids into cific surface area, pore diameter and pore volume of
the slurry and maintenance of the slurry at a suitable microspheres were determined by the BET technique.
temperature for a sufficient time. In the present study, The topography of the microspheres was examined by
the gel was peptized by HNO3 addition in a vessel at SEM. TGA measurements were carried out to deter-
80 °C for 3 h to produce a stable sol. mine the weight loss before and after calcination. The
crystal structure of microspheres was characterized by
1.3. Gel formation and preparation of microspheres X-ray diffraction.

The sol obtained after acid peptization of the hydrol-

2. Experimental
ysis product is gelled by adding a suitable electrolyte
which screens the positive surface charge of the col-
2.1. Materials
loidal particles [15,16]. In the present study, the sol was
introduced through a hypodermic needle as droplets A Dispal alumina sol and aluminum monohydrate
which slowly dehydrated from contact with an organic (boehmite (AlOOH)) manufactured by Vista Chemical
liquid (mineral spirit) which is used to preserve the Company were used as starting material.
shape of sphere and converted into solid gel micro-
spheres in contact with NH4OH solution. Thus, the 2.2. Production of microspheres
microspheres do not agglomerate and can be collected
and subjected to heat treatment for converting the A hypodermic needle (size: 0.45 mm) and 5 ml sy-
hydroxides into oxides. ringe were used to generate droplets of the desired size.
The optimum viscosity of alumina sols is between 5 The sol was added dropwise to a gelation container
to 7 mPa s at 25 °C to prepare microspheres. If the (150 ml beaker) filled with 60% v/v NH4OH/mineral
viscosity is lower than this optimal range, nonuniform spirits mixture. Gelation time is very short, requiring
spheres will form. If it is higher than 70 mPa s, it is only 1–2 min. The spheres were quickly transferred
more difficult to form droplets. into a container, washed two times with ethyl alcohol,
Gelation time is a critical processing parameter to then dried in vacuum for 24 h. After dehydration, the
obtain low density and porous spheres. Density of microspheres have sufficient strength that they were
spheres increases with increasing gelation time [7,16]. placed in a tray for insertion into a calcining furnace.
After gelation, the removal of solvent decreases the Microspheres were calcined at 600 and/or 1000 °C for
size of the gel. Drying procedure is most important 2 h with slow heating rate (2 °C) to convert the hy-
since the removal of solvent leads to the development droxides into oxides without additional shrinkage. The
of capillary forces. If the evaporation and diffusion of sol –gel processing sequences for producing micro-
solvent molecules out of the bulk gel is too fast, shrink- spheres of alumina are given in Fig. 1a.
ing effects lead to cracks. The fractures associated with Secondly, aluminum monohydrate (bohemite
excess capillary forces can be reduced or eliminated by (AlOOH)) which was purchased from Vista Chemical
several procedures. In general, evacuating the solvent Company was used to prepare microspheres. The alu-
by freeze drying produces dried gels with much larger mina sol was prepared by dispersing 10 g of the
pore volumes than conventional evaporation drying. AlOOH powder slowly into 40 g of distilled water while

Fig. 1. (a) The sol – gel processing sequences for producing microspheres of alumina. (b) Summary of the processing procedures starting from the
alumina sol leading to the fabrication of uniform porous spheres. Schematic diagram illustrating sol-gel process for producing microspherers of
alumina.
N. Dilsiz, G. Ako6alı / Materials Science and Engineering A332 (2002) 91–96 93

Fig. 1.
94 N. Dilsiz, G. Ako6alı / Materials Science and Engineering A332 (2002) 91–96

XRD measurements were carried out for each sample

to characterize the structure of microspheres. SEM
studies were also conducted to examine the fracture
surface of microspheres.
Thermogravimetric analyses were obtained using a
DuPont 2000 and a Netzsch thermal analyser. Samples
were decomposed in a nitrogen atmosphere at a con-
stant heating rate of 10 °C min − 1.

3. Results and discussion

3.1. Characterization of microspheres

3.1.1. SEM results

As shown in Fig. 2a,b, the alumina spheres produced
with the present method are quite uniform in size.
Large alumina spheres (2 mm diameter) were prepared
by dropwise addition of sol into the gelation container
that are given in Fig. 2a. Particle size and generation of
spheres can be varied by adjusting flow rates of sol
emanating from the hypodermic needle. By applying
pressure to produce a stream of sol, particles less than
1mm diameter can be prepared (Fig. 2b). The SEM
micrographs of fracture surfaces of alumina spheres at
different magnification are shown in Fig. 3a,b. Electron
micrographs indicate that pores are present and dis-
tributed throughout the surface.

3.1.2. BET results

The surface area of microspheres was derived from
adsorption isotherm for nitrogen in liquid nitrogen.
Fig. 2. The SEM micrograph of alumina spheres of different diame-
ters produced with drop generation method. (a) 1 – 1.5 mm diameters, Table 1 represents the physical properties of samples
(b) 0.5 – 1 mm diameters. (A, B, C and D) which are the BET specific surface
area, pore volume, and average pore diameter, respec-
stirring. The water temperature was 85 °C. After an tively. From Table 1 it can be seen that the surface area
additional 15 min of mixing 0.3 g of concentrated nitric of spheres calcined at 600 °C (sample B) is higher than
acid (HNO3) (70%) was added to the solution. This that of spheres at 1000 °C (sample C). The surface area
addition was done very slowly to avoid foaming. When decreases from 199 to 107 m2 g − 1 for sample B and
the acid addition was completed, the sol was stirred for sample C, respectively. The nitrogen adsorption
another 3 h at 80 °C. After that, the same procedure isotherm of sample B is given in Fig. 4.
which was mentioned above was used to prepare alu- The calculated pore volumes and pore size are also
mina spheres. given in Table 1. The smaller size spheres have larger
Experimental details are given in Fig. 1b which surface area. The pore volume and pore diameter de-
shows a schematic diagram of the sol– gel process for creased with decreasing particle size. The diameters of
producing microspheres of alumina. pores were in the range of 24.7–10.7 A° for samples B
and D, respectively.

2.3. Sample characterization 3.1.3. Density measurements

The density measurement results are also given in
The surface area, pore volume, and average pore Table 1. The lowest density (1.5 g ml − 1) was obtained
diameter of alumina microspheres were determined by when the microspheres were calcined at 600 °C. The
nitrogen adsorption isotherm by using Quato Chrome density of alumina spheres increases with increasing
Monosorb BET instrument. The average diameter and calcination temperature. The firing of gel leads to den-
pore volume were calculated by using Kelvin equation sification of the structure due to collapse of pores in the
[17]. structure.
 N. Dilsiz, G. Ako6alı / Materials Science and Engineering A332 (2002) 91–96 95

Table 1
Physical properties of microspheres prepared by sol–gel process

Dried particle Density (g ml−1) in Specific surface area Pore volume Average pore TGA weight loss
diameter (mm) decane (0.73 g ml−1) (m2 g−1) (multiple (ml g−1) diameter (A°) (%) (50–800 °C)
point measurement)

1–2 Sample A uncalcined 20.85

dried alumina
1–2 Sample B (calcined 1.5–2.0 199.05 0.12 9 0.02 24.70 94.20 5.09
at 600 °C)
1–2 Sample C (calcined 2.0–2.5 107.05 4.39
at 1000 °C)
0.5 Sample D (calcined 1.5–2.0 351.85 0.09 90.01 10.76 90.84
at 600 °C)

3.1.4. Thermogra6imetric analysis

Thermogravimetry analysis of microporous uncal-
cined alumina shows a significant weight loss of 20%
due to loss of water and alcohol below 500 °C and also
indicates essentially complete pyrolysis at about
500 °C. There is a continous, but small weight loss with

Fig. 4. The nitrogen adsorption isotherm of alumina spheres (sample

B).

increasing temperature, attributed to loss of water from

surface hydroxyl group. Thermogravimetric curves indi-
cate that a total weight loss about 5% occurs for the
alumina spheres calcined at 600 and 1000 °C.
1. 100–200 °C desorption from the micropore walls of
physically adsorbed water
2. 300–500 °C decomposition of organic compound
3. 400–600 °C collapse of small pores
4. 600–1000 °C collapse of large pores

3.1.5. XRD results

Alumina microspheres were examined by XRD. X-
ray diffraction of microporous alumina which were
calcinated at 600 and 1000 °C shows only broad reflec-
tions which probably indicate very small crystals.

4. Conclusion

This study has demonstrated the making of uniform,

porous alumina spheres of controlled size and porosity
by combining a drop-generation technique with sol–gel
Fig. 3. The SEM micrograph of fracture surface of alumina spheres at processing. Alumina spheres with surface area 351 m2
low magnification: (a) × 2500, (b) × 50 000. g − 1 and pore size 10.7 A° have been prepared by using
96 N. Dilsiz, G. Ako6alı / Materials Science and Engineering A332 (2002) 91–96

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[8] L. Montanaro, B. Guilhot, Ceram. Bull. 68 (5) (1989) 1017.
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