Journal of Sol-GelScienceand Technology,3, 117-126 (1994)

© 1994 KluwerAcademicPublishers,Boston. Manufacturedin The Netherlands.

Preparation of Alumina by Sol-Gel Process, Its Structures and Properties

S. SAHA
Chemical Processing and Development Section, Powder Metallurgy Division, Bhabha Atomic Research Centre, Turbhe, New Bombay 400 705, India

Abstract. Alumina monolithic gel has been prepared by ammonia method from anhydrous aluminium chloride and
n-butanol using formamide as the solvent. The gel has been made by hydrochloric acid catalysis and using large
quantity of water for hydrolysis (molar ratio of water to aluminium-n-butoxide, R > 99). Transparent alumina
xerogel of size 37.5 x 20 x 5 mm approximately has been prepared. The alumina gel has been dried and sintered
at 400°C, 1000°C and 1200°C respectively and the powders formed thereby have been examined by XRD, FTIR
spectroscopy, SEM and particle size analysis. These studies have confirmed the formation of a-alumina at 1200°C
having particle size as low as 0.2 #m or less along with agglomerates. The density of the powder has increased
gradually, where as its particle size has decreased, with the increase of the sintering temperature.

Keywords: alumina monolithic gel, ammonia method, formamide as solvent, submicron size a-alumina particles

1. Introduction excluding aluminium e.g. silicon, germanium, tita-

Alumina is one of the most important technical ceram-
ics. It has versatile uses, such as lasers, lamp cov-
ers, threadguides, catalytic converters and substrates
for microelectronic computer chips. Yoldas [1-3] syn-
thesized monoliths of alumina by sol-gel technology in
which the sol precursor used was an aluminium alkox-
ide. Yoldas process consists of four steps: (1) hy-
drolysis of aluminium alkoxides, (2) peptization of the
hydroxide to a sol, (3) gel formation and (4) pyrolysis
of the dried gel to alumina.
Aluminium alkoxide precursor required to use in
Yoldas process can be made by a number of ways.
Gladstone and Tribe [4] prepared aluminium triethox-
ide by the reaction of aluminium metal with ethanol
using iodine as a catalyst.
I2
A1 + 3C2HsOH --* AI(OC2H5)a + 3/2H2
Aluminium tris-isopropoxide is synthesized by the Ad-
kins and Cox [5] method.
HgCI 2
AI + 3C3HTOH e x o t h e r m~i c AI(OC3HT)3
+ H g + 2HCL + ~H2 1 2.1. Preparation of Transparent Alumina Xerogel
nium, zirconium, hafnium, niobium, tantalum, iron,
antimony, vanadium, cerium, uranium, thorium and
plutonium from their chlorides and appropriate alco-
hol [10].
In this paper, a method is described by which
aluminium-n-butoxide has been prepared from anhy-
drous aluminium chloride and n-butanol using for-
mamide as solvent in presence of anhydrous ammonia.
The alkoxide thus obtained has been used to prepare
monolithic alumina xerogels by Yoldas process. The
alumina gel has been sintered at 400°C, 1000°C and
1200°C and the powders obtained thereby have been
examined by X-Ray Diffraction (XRD), Fourier Trans-
form Infrared (FTIR) spectroscopy, Scanning Electron
Microscopy (SEM) and particle size analysis. Where
XRD and FTIR spectroscopic studies have indicated
changes in crystal structure with the rise of tempera-
ture, SEM and particle size analysis have characterised
the size, morphology and distribution pattern of the
particles.
2. Experimental

But the ammonia method [6-8], which is the most eco- For the preparation of alumina gel, aluminum-n-
nomic and simple [9] for large scale production, has butoxide was prepared from anhydrous aluminium
so far been used to make a large number of alkoxide chloride and n-butanol, using formamide as the sol-
118 Saha
90
70
h-
,s,
m
o. so-
30-
'~o is 3'o 3's
Fig. 1. X-ray diffraction pattern of alumina sintered at 400 o C.
vent, in presence of anhydrous ammonia. Aluminium
chloride was dissolved in formamide. Undissolved
matters were filtered out. The solution was cooled in an
ice bath to 5 ° C and n-butanol was added when simulta-
neously ammonia gas was passed slowly into the solu-
tion, maintaining the temperature at 5°C. Large excess
of water in the ratio of about 99 moles water/mole of
Al(OC4Hg)3 was added to hydrolyse the alkoxide. It
was centrifuged. The residue was separated and the
clear solution containing ammonium chloride was dis-
carded. The residue was washed with water eight times
stirring with same proportion of water followed by cen-
trifuging to remove the ammonium chloride. After last
wash, the final slurry was peptized (polymerized) with
0.07 mole hydrochloric acid/mole of AI(OC4Hg)3 heat-
ing at 80°C. Finally the mixture was boiled till gel was
formed. The gel was casted on a polythene sheet placed
over a glass petridish. The casting was kept inside a
calcium chloride desiccator where drying was allowed
to take place for 110 hours when transparent alumina
xerogel was obtained.
In a typical experiment, 15 g anhydrous aluminium
chloride was dissolved in 150 ml of formamide and 15
ml of n-butanol was added along with ammonia gas.
Subsequently 200 ml of water was added to this reac-
tion mixture to hydrolyse aluminium alkoxide.
/I
~'o 4s s'o ~5 4o ds 710 75 50
2 THEJA (~ATE)
2.2. Heat Treatment of Alumina Gel and Powder
Characterisation
The dried alumina gel was pyrolysed at 150°C for 2
hours followed by another two hours at 400°C inside
a muffle furnace. Platinum crucible was used through
the heat treatment for holding the alumina. A sample
was collected after heating the alumina at 400°C. The
balance part of it was further sintered at 1000°C and
1200°C respectively in an induction furnace for 1 hour
each and samples of both were collected for character-
isation. All the three samples were ground in an agate
mortar and pestle to make powders. Specific gravity
of the transparent xerogel and the powders obtained
from 400 °, 1000 ° and 1200 ° were found out using a
specific gravity bottle. XRD was done by Diano, Se-
ries 2000, USA and FTIR spectroscopy was done by
Mattson, Sygnus 100, USA models of instrument to
find out phase transformations of the sintered alumina
samples. Shape, size and distribution pattern of the
powders were found out by SEM (model: Cambridge
instrument, Sterioscan S-240, UK) and Horiba LA-500
model, Japanese particle size analyser.
Initial pyrolysis at 150°C was done to drive out or-
ganic matters which otherwise could char at the subse-
quent heating at elevated temperatures. Platinum cru-
 Preparation of Alumina by Sol-Gel Process 119

82 i
80-~

P.
70 ¸ g~

~n

w
o_
I

20.

10-

!
O ~
2O ~'5 3'0 ~'s 2o 4's 40 s'5 6d is 70 75 80

"2 X~ETa ~RaTE )

Fig. 2. X - r a y diffraction pattern o f a l u m i n a sintered at 1 0 0 0 ° C.

cible and agate mortar and pestle were used to avoid
any cross contamination which could affect the XRD,
infra-red and SEM analysis. For particle size analy-
sis, the powders were ultrasonically treated, for half
an hour each, in 0.1% aqueous solution of calgon for
dispersing the particles. FTIR samples were made in
3% KBr by pressing to discs.
The temperatures in the muffle furnace were mea-
sured by a thermocouple whereas those in the induction
furnace were measured by a two-colour optical pyrom-
eter.
3. Results
Figs. 1-3 show the XRD patterns of alumina powders
sintered at 400°C, 1000°C and 1200°C respectively.
FTIR spectroscopy graphs of these samples are indi-
cated in Figs. 4-6. From Fig. 7 the size and morphology
ofsintered alumina (1200°C) can be seen. Particle size
analysis graphs are depicted in Figs. 8-10 in ascend-
ing order of sintering temperatures. Table 1 indicates
how sintering at higher temperature has contributed to
increase the density of the powder.
The d-values with percentage intensities are indi-
cated on the top of each peak in Figs. 1-3. The peak
with largest counts per second has been depicted as the
100 percent intensity in all these figures. The wave
number and percent transmission are indicated against
each peak of the FTIR plots in Figs. 4-6. The magnifi-
cation of image in Fig. 7 of SEM analysis is 5120 times.
In particle size distribution graphs of Figs. 8-10, the
abscissa is the size of particles in micrometer where as
F % is the percent fraction in weight of each span of
particle size indicated by vertical rectangles and U%
is the cummulated weight fraction of particles. These
figures indicate the particle size distributions measured
at a particular instant from the suspension. The distri-
bution of the same sample may vary a little if different
readings are taken. The median value of particle size,
specific area of the sample, weight percent of particles
of diameter, 2.1 #m present in the sample and diameter
of 90% particles are shown in these figures.
4. Discussion
4.1. Aluminium Alkoxide by Ammonia Method to
Form Alumina Gel
The reaction that has taken place to form aluminium-
n-butoxide is as follows:
120 Saha

420-

400-

¢o

350 $

300-

25O-

8 S
,,I
a_

100-

50"

O~
20 40 65 70 75

2 T H E T A ( RATE')

Fig. 3. X-ray diffraction pattern of alumina sintered at 1200 ° C.

MICROlNg
z,~ 3.0 3,5 4-0 5-0 6-0 a lo 15 20
I I I I I I I I I

24 2346"82 5 cm'l /'~ / ~

% 22
T
R 20
A
18'

t 16
5
S
14
0
N 12

10.

8 -

I [ I ] I I I
40O0 350 0 3000 2500 ? 000 1500 1000 500
WAVE NUM~E~

Fig. 4. FTIR graph of alumina sintered at 400 o C.

 Preparation of Alumina by Sol-Gel Process 121

MICRONS

2.5 3'0 3"5 4,0 5.0 6+0 8 10 15 20

% __ I __ I 1 I I ........ i I I I

65-
T
R 60-
A
hi 55-
S
M 50-
I
S 45-
S
I 40- ~ ~ ~ 762+452 cm-I
0 ' ~ / ~ ...... v --'---~ \;~.o542 .,. T
N '+-

3o- / I ..... 1_ ~ ~6,666m

i / +b~'bJuc,.'.-, \ \ ~lo.35ss't.T)

20[ 37,3073"/. _ 825+65"7cm-1 X~ X /~

I I ' J . . . . . . . . .
4000 3500 3000 25()0 2000 1500 1000 500

WAVE NUMBER

Fig, 5, FTIR graph of alumina sintered at 1000°C+

MIEREINB
2.5 3.0 3.5 4.0 5.0 6.0 15 I0 15 20
I ..... i i__ I ,I ...... I l I I

~ 1376,21~2
era-I
%, 55 _ -1 4791 */,, T

4o _ ~ + 2 . =o ~.,-I . " + ~ + m+, ,:.,~-f

46,3864 "],T
~/'1438" 860 ¢m-]
54+02 97 "I,T
45-4438 % T // "
35

30_

2O 455,926 cm+l
.--vggz%-~1+
i+ T

4000 3 500 3000 25OO 2000 1500 lOOO .: 500

WAV E N U M B E R

Fig. 6. FTIR graph of alumina sintered at 1200°C.

122 Saha

Fig. Z SEM micrographof alumina sintered at 1200°C.

Table 1. Specificgravity of gel and sintered alumina. Sidgwick [14] postulated that for electronegative ele-
ments like boron, silicon and phosphorous, solvolysis
Sr.No. Sample Specific gravity of the chloride might occur through initial coordina-
tion of the alcohol followed by elimination of hydrogen
1 Aluminamonolithic xerogel (Dried) 1.722
2 Aluminapowder sintered at 400° C 1.966 chloride as shown below:
3 Aluminapowder sintered at 1000°C 2.405
4 Aluminapowder sintered at 1200°C 3.t59 R C1

O-~B--CI
(-He,) I [
HCONH2
' O-~B --C1
A1C13 + 3 r t - C n H g O H + 3NH3 5o c ) I I
Al(OC4H9)3 + 3NH4C1 R' ola
.~ (-Hel)
Conventionally, benzene or toluene [9] is used as the OR OR
solvent to dissolve anhydrous metal chlorides of tita- I I
nium, zirconium and hafnium etc. for the prepara- RO~B ~.and
..... so on B --Ct
tion of their corresponding alkoxide. Anhydrous alu-
I
OR OR
minium chloride cloes not dissolve appreciably in ben-
zene. Moreover it remains as a dimer in this solvent.
Boron and aluminium are two consecutive elements of
group IIIa of the periodic table having the same outer-
A12C16 ~ 2A1Cla; C1 C1 C1
\ / \/ / most electron orbit configuration a s s 2 p 1 . So the above
A1 A1 mechanism of boron alkoxide formation should hold
/ /\ / \ good for aluminium also. But aluminiumbeing dimeric
C1 C1 C1 in benzene, co-ordination as per the sidgwick mecha-
 Preparation of Alumina by Sol-Gel Process 123

I + i i , , l l r l

10 100 I0 100

F 'I, U% F "I, U%

5 50

0 O[ I I + Ill[ "" g I I (IIIH I I IFILLLI I

0.1 1 10 100 200 0,1 1 I0 100 21313

SIZE /urn SIZE ,urn
MEDIAN : 10.74~m "/o ON DIA{ 2 - t / u r n = 5,2 "/° MEDIAN : 21,zi5,um "/. ON DIA : 2.1)u m = 2,1 "I.
SRAREA 8761 cm2/cm 3 DIAON°Io ~+90-0"/o : 33.%01Jm SPAREA : 5081 cm2/'crn~ DIA ON'/,: 900"/.= 57-39,AJm

Fig. 8. Particle size distribution of a l u m i n a sintered at 4 0 0 ° C. Fig. 9. Particle size distribution o f a l u m i n a sintered at 1 0 0 0 ° C.

nism to eliminate HC1 is hindered. Moreover, the activ- 10 --

I I [ Illlll [ I i [JlliI - - [ I I I I [ l / r ~
1 O0
ity of chlorides of elements of the same group is found
to decrease with increasing electropositive character. F "1. U "I,

Aluminium is more electropositive than boron. So, an-

hydrous aluminium chloride, in benzene medium, did
not respond to the ammonia method to form the alkox- 5O

ide with n-butanol.

Formamide was found to be a suitable solvent
to dissolve anhydrous aluminium chloride. In this
favourable medium, ammonia reacted as a base to in-
0 11 ~ ~ 'l'l'l'li --" " ~ " I ~ "1 [ J L I l 1 t II[lll __ 0
crease the concentration of alkoxide anions which then 0,1 l 10 100 200
reacted with the aluminium chloride as indicated be- SIZE Nrn
low: MEDIAN z 17,55 /urn "/.ON DIA ; 2,1)um ~ 15.g "/o
SP, AREA 22992¢mT/cm 3 DIA ON % ; 90"0°/o :51.51/IJm
3NH3 + 3n-BuOH ~ 3NH + + 3(OBu)- Fig. 10. Particle size distribution of a l u m i n a sintered at 1 2 0 0 ° C .
C1 OBu
I with HC1 helped remarkably to diminish the formation
3 ( 0 B u ) - + AI-C1 > A1-OBu + 3C1-
I I of cracks in the castings. Thus, a maximum size of
C1 OBu 37.5 x 20 x 5 mm alumina gel as shown in Fig. 12
3NH + + 3C1- ~ 3NH4C1 was prepared.
The above reaction is exothermic. The reaction mixture
was kept at the low temperature (5°C) using a mixture
of ice and common salt. Normal butanol was used in
4.2. XRD and FTIR Spectroscopic Analysis of
stead of more common sec-butanol for the preparation Sintered Alumina
of alkoxide. The reaction taking place during hydroly-
sis, polymerization and pyrolysis are shown in Fig. 11. Preheating of the gel was done at 150°C prior to sinter-
Fig. 12 shows the transparent alumina xerogel dried ing to avoid carbon contamination. Figs. 1-3 signify
in a desiccator at ambient temperature. Crack forma- gradual transformation of amorphous alumina to crys-
tion during drying has posed a major problem to get dry talline forms. XRD data also indicate formation of (5-
transparent gel. However, casting the gel on polythene A 1 2 0 3 , mixture of 0-A1203 and r-A12 0 3 and a-A12 03
sheet and then drying it inside the calcium chloride phases at 400 °, 1000 ° and 1200°C respectively. These
desiccator have been found effective to avoid multiple phase transformations of alumina are similar to those
cracks. Further, addition of glycerol before peptization reported in the literature [11].
124 Saha

HYOROLYSI$

~O°C
AI(OC4H9) 3 + HzO 9 AL(0C4Hg) 2 (OH) + C4HsOH
Alu~ini~-n-butoxide n-butanol

pOLYI~ERIZATION

OH OH
lIUl
I I
z AI(0C4H9) z (OH) + Ha0 C&H90-AI-O-AI-OC4H S ÷ 2C4HgOH
n-butan~l

PYROLYS IS

Dried Gel
4OO°o
A~ o(o~) - > 6 - AIzO 3 + Ha0
6-AIzO 3 Monohyd~a%e

1000°d IZ00°O
g - AIzO 3 > ~ - AIzO 3 + F A ] z O 3 -- > ~ - AI203

Fig. 11. Hydrolysis, polymerization and pyrolysis reactions in A1203 derived from aluminium-n-butoxide peptized with HC1.

The FTIR graphs in Figs. 4 - 6 signify removal of
water in the sample with the increase in sintering tem-
perature. The peaks 2790.005 cm -1 - 2947.99 cm -1
and 2346.825 cm -1 - 2355.904 cm -1 of Figs. 4 &
5 corresponding to carbon-hydrogen bond and carbon
dioxide respectively are not seen in Fig. 6. This is
due to the absence of organic matters in the sample at
1200°C. The peaks 455.926 c m -1, 608.844 cm -1 and
644.894 c m - 1 of Fig. 6 are similar to those reported
by Clark et al [12] for gel derived alumina at 1300°C.
The a-phase of the alumina sample sintered at 1200°C
is found to be characterised by nine peaks both in FTIR
spectroscopic and XRD analysis.
4.3. SEM and Particle Size Analysis of Sintered
Alumina
The distribution graphs (Figs. 8 & 9) of alumina par-
ticles sintered at 400°C and 1000°C are similar. In
none of these two cases sub-micron size particles are
significantly present. But Fig. 10 indicates that the sub-
micron size particles present in this case is quite signif-
icant. That is why the specific area (22992 cm2/cm 3)
for 1200°C sample is quite high as compared to
8761 cm2/cm 3 or 5061 cm2/cm 3 in other two cases.
The maximum size of particles present in 1200°C sam-
ple is also only about 150 # m as compared to 200 # m

Fig. 12. Transparentaluminaxerogel.
in other two cases. From all these, it becomes clear
that true size of the particles formed is in sub-micron
level where as other particles are only their agglom-
erates. SEM analysis also confirms this as shown in
Fig. 7. In this figure it is seen that the smallest par-
ticles are in sub-micron level. Fig. 10 indicates that
the size of smallest particles present in the sample sin-
tered at 1200°C is about 0.1 #m. But in Fig. 7 smaller
particles than 0.1 #m are also found to be present. For-
mation of particles of such small size is in accordance
with the observations reported by other workers [13]
who adopted sol-gel process for the preparation of ce-
ramic powders.
From Table 1, it is seen that the specific gravity
of transparent alumina xerogel is 1.722 and it has in-
creased by sintering the gel at a higher temperature to
reach a maximum at 1200°C.
5. Conclusion
Ammonia method of preparation of aluminium-n-
butoxide and preparation of transparent alumina xero-
gels from this alkoxide have been demonstrated. This
alumina gel was sintered at different temperatures when
Preparation of Alumina by Sol-Gel Process 125
phase transformations took place finally forming c~-
alumina at 1200°C which is in conformation to the
observations made by other workers in sol-gel technol-
ogy. The particle size of the sintered alumina powders
were ascertained. The size of the particles was in sub-
micron range which is a characteristic feature of sol-gel
process. Being a simple method, this process of pro-
duction of alumina powder will help further progress
of alumina ceramics.
Acknowledgments
The author gratefully acknowledges the support ex-
tended by Shri B.R Sharma, Head, Powder Metallurgy
Division, BARC for setting up the facility for this work.
He also acknowledges the sincere work done by his col-
league Shri B.E Mistry in this programme.
References
1. Yoldas,B.E., Alumina Sol Preparation from Alkoxide, Am.
Ceram. Soc. Bull. 54(3), 289-290 (1975).
2. Yoldas,B.E.,A TransparentPorousAlumina,Am. Ceram.Soc.
Bull. 54(3), 286-288 (1975).
126 Saha
3. Yoldas, B.E., Alumina Gels That Form Porous Transparent
A1203, J. Mater. Sci. 10, 1856-1860 (1975).
4. Gladstone, J.H. and Tribe, A., J. Chem. Soe., 39, 4(1981).
5. Adkins, H. and Cox, J., J. Amer. Chem. Soc., 60, 1151 (1938).
6. Bradlay, D.C., Mehratra, R.C., and Gaur, D.E, Metal Alkox-
ides, Academic Press, New York, pp. 19-21 (1978).
7. Mazdiyasni, K.S., Lynch, C.T., and Smith, J.S., J. Amer. Ce-
ram. Soc., 50, 532 (1967).
8. Bradley, D.C.. Mehratra, R.C., and Wardlaw, J., Chem. Soc.,
London, 1963 (1953).
9. Mazdiyasni, K.S., Chemical Synthesis of Single and Mixed
Phase Oxide Ceramics, Mat. Res. Soc. Symp. Proc., Vol. 32,
Elsevier Science Publishing Co., 176 (1984).
10. Bradley, D.C., Mehratra, R.C., and Gaur, D.E, Metal Alkox-
ides, Academic Press, New York, p. 20 (1978).
11. Clark, D.E. and Lannuti, J.J., Phase Transformations in Sol-
gel Derived Alumhlas, Ultrastructure Processing of Ceram-
ics, Glasses and Composites, Interscience Publication, USA,
pp. 126-141 (1984).
12. Ibid, p. 136.
13. Mazdiyasni, K.S., Chemical Synthesis of Single and Mixed
Phase Oxide Ceramics, Mat. Res. Soc. Symp. Proc., Vol. 32,
Elsevier Science Publishing Co., 180 (1984).
14. Sidgwick, N.V., J. Chem. Soc., 125, 2672 (1924).