Volume 6, number

I 1,12

MATERIALS

July 1988

LETTERS

A NOVEL COMBUSTION PROCESS FOR THE SYNTHESIS OF

FINE PARTICLE a-ALUMINA AND RELATED OXIDE MATERIALS
J.J. KINGSLEY

and K.C. PATIL

Department of Inorganic and Physrcal Chemistry, Indian Institute ofScience.

Received

Bangalore

560 012, India

25 April 1988

Synthesis of tine particle a-alumina and related oxide materials such as MgA120,, CaAl,04, Y,Al,0i2
(YAG), t-ZrOz/Al,02,
l3-alumina, LaAlO, and ruby powder (Cr3+/Al,03)
has been achieved at low temperatures
(SOOC) by the combustion of corresponding metal nitrate-urea
mixtures. Solid combustion products have been identified by their characteristic
X-ray diffraction
patterns. The tine particle nature of a-alumina and related oxide materials has been investigated using SEM, TEM, particle size
analysis and surface area measurements.

1. Introduction
Alpha alumina and related oxides are of interest
due to their technological applications as abrasives
and refractories [ 1 ] (a-alumina,
MgA1204), lasers
[ 2,3 ] (ruby, NdYAG), solid electrolyte [ 41 ( P-alumina), high alumina cement [ 5 ] ( CaA1204 ), toughened ceramics [ 6 ] ( t-ZrOz/A1203 ), and catalysts [ 7 ]
( LaAlO, ). The most common method of preparing
these oxide materials is by the ceramic method involving the reaction of component oxides at elevated
temperatures. The ceramic method suffers from several disadvantages and it is difficult to obtain a compositionally homogeneous product. The importance
of preparing micron size ceramic powders [ 8 ] in sintering and fabrication of materials with controlled
microstructure
and desired shape need not be emphasised. Various other methods like freeze drying,
spray drying, coprecipitation
and sol-gel techniques
have also been employed to obtain these ceramic
powders. The synthesis of some oxide materials like
ferrites in a state of high purity and homogeneity at
far lower temperatures
than the conventional
ceramic method is achieved by the precursor method
[ 9, lo]. The emphasis in all these methods is in
achieving the synthesis at low temperatures
so that
the products obtained are in a finely divided state
with large surface areas. Here, we report for the first
time the synthesis of micron size a-Alz03 and related
0167-577x/88/$
( North-Holland

03.50 0 Elsevier Science Publishers

Physics Publishing Division )

oxide materials by the combustion of corresponding

metal nitrate-urea
mixtures at a low temperature of
500C in less than 5 min. The high temperature required for the formation of these oxides is achieved
by the exothermicity of the redox reactions between
the decomposition
products of metal nitrate (oxidizer) and urea (fuel) during combustion. The process is safe, simple and instantaneous.

2. Experimental
Stoichiometric
compositions of the metal nitrates
(oxidizers) and urea (fuel) were calculated using the
total oxidizing and reducing valencies of the components which serve as numerical coefficients for
stoichiometric
balance so that the equivalent ratio
(@,) [ 111 is unity and the energy released by the
combustion is at a maximum. The stoichiometric ratios arrived at by this approach for the mixtures containing mono-, di-, and tri-valent metal nitrate and
urea are 1:0.833, 1: 1.666 and 1:2.5 respectively.
In a typical experiment, aluminium nitrate (20 g)
and urea (8 g) in the mole ratio 1:2.5 were mixed
in an agate mortar (or dissolved in minimum quantity of water) and the resulting paste (solution) was
transferred into a cylindrical Pyrex dish ( 100 mm
diameter and 50 mm height) of = 300 ml capacity.
The dish containing the paste (solution)
was introB.V.

427

Volume 6, number 11,12

July 1988

MATERIALS LETTERS

Fig. 1. a-Al,Oj foam as formed (weight 2.72 g, volume 300 cm3).

duced into a muMe furnace (I= 28 cm, b= 17 cm and

h= 9 cm) maintained at 500 k 10C. Initially, the
paste (solution) melts (boils) and undergoes dehydration followed by decomposition with the evolution of large amounts of gases (oxides of nitrogen
and ammonia). The mixture then froths and swells
forming a foam, which ruptures with a flame and

glows to incandescence. During incandescence the

foam further swells to the capacity of the container.
The entire combustion process is over in less than 5
min. The duration of the flame is about 2 min. The
flame temperature as measured by a disappearing filament optical pyrometer is around 1600 k 20 C. The
product of combustion (fig. 1) is voluminous and
foamy a-alumina (weight 2.72 g, 100% yield) having a tap density of 0.09 g/cm. These high-temperature combustion processes could be carried out in
Pyrex glass containers due to the heat insulating
properties of a-alumina and its related oxide materials. The compositions used for the combustion synthesis of other oxide materials such as Y,Al,O,,
(YAG), MgA1204, CaA1204, t-ZrGz/A1203, P-alumina and LaAlO, are given in table 1.
X-ray powder diffraction patterns of the combustion products were recorded using a Philips X-ray
diffractometer model PW 1050/70 using Cu Ku radiation with Ni filter. The powder densities of all the
oxide materials were measured using a pycnometer
with xylene as a solvent. The surface area measurements were made by nitrogen adsorption employing
a Micromeritics AccuSorb 2 1OOE instrument. Particle size analysis was done using a Micron Photosizer model SKC 2000 based on light scattering
principle employing sedimentation. The macrostructure and morphology of a-alumina and t-ZrOJ

Table 1
Compositions of the combustion mixtures and the properties of their combustion products
No.

Particle size
(from surface
area)
(um)

50% average
agglomerate size
(from sedimentation) (urn)

8.30

0.22

4.3

3.86

7.30

0.21

4.5

MgAJzOd

3.00

21.80

0.10

5.2

CaAIZO,

2.48

1.25

1.92

4.1

t-ZrOz/Al203 b,

4.07

3.12

0.47

4.7

S-A1203C)

3.40

50.80

0.03

4.2

LaAIOJ

5.30

3.00

0.37

4.0

Compositions of the
combustion mixtures

Products )

Powder
density
(g/cm3)

20gAl(N0,),.9H20and8gurea
20 g Al(N03),.9HZ0, 12.8 g urea and
12.25 gY(NO,)3.6HzO
20 g AI(N09)3.9HZ0, 10.7 g urea and
6.83 g Mg(NOX)?.6H20
20gAl(N03),.9H20,
10.7gureaand
6.29 g Ca(NOJ)2.4H20
20gAI(N09)9~9H20,9.10gureaand
2.75 g ZrO(N03)r.HrO
20 g Al(NOI)3.9H20, 8.20 g urea and
0.823 g NaNO,
20 g A1(N09),.9Hz0, 16.0 g urea and
23.08 g La(N09)r,6H20

a-Al,Os

3.21

Y~A&OII (YAG)

a Obtained at 500C and normal atmospheric pressure.

428

b, 50 wt% ZrO2 in AllOr.

Surface
area (BET)
(m*/g)

) Na*0.7.22 A1203.

Volume 6, number 11,12

July 1988

MATERIALS LETTERS

AllO3 were studied using a Cambridge Steroscan

model S- 150 scanning electron microscope (SEM)
and a Philips EM 301 transmission
electron microscope (TEM ) operated at 100 kV. The excitation and
emission spectra of the ruby powder were recorded
using a Hitachi 650-60 fluorescence
spectrophotometer.

11111
(a)

(b)

3. Results and discussion

Actual compositions used for the combustion synthesis of u-alumina and related oxide materials, the
density and particulate properties of the solid combustion products are summarised in table 1. Typical
X-ray powder diffraction (XRD) patterns of the asprepared a-A&O,, Y3AlS0,2 (YAG), t-ZrOz/A1203,
p-alumina, MgA1204 and LaA103 are shown in fig.
2. These XRD patterns are similar to those reported
[ 121 in the literature for the respective oxides confirming the formation of single-phase products. The
lattice constants calculated from the XRD patterns
of a-A1203 (a=b=4.7719(5)
8, and c= 13.0426(7)
A) and MgAl*O, (a=& 1153 A) are also in good
agreement with the literature [ 12 1. The XRD pattern of b-alumina
closely resembles
that of
Naz0.7.02A1203
[ 131. The surface area of these oxides varies from 1 to 50 m2/g, p-alumina having the
highest value of 50.8 m*/g. The pore size analysis of
the oxide materials was carried out using the adsorption isotherms. It was observed that the oxides
have micropores with a narrow pore size distribution of lo- 100 A. The values of powder densities of
the oxide materials (table 1) correspond to nearly
80% of the theoretical densities. The SEM micrographs (figs. 3a and 3b) show the macrostructure and
the surface of the u-A1203 foam respectively. The
foamy structure of a-A120, reflects the inherent nature of the reaction. The presence of solid phase can
be seen in the cellular walls of the foam. The surface
of the foam (fig. 3b) shows cracks, voids and
pores formed by the escaping gases during the combustion. The TEM micrographs of a single particle
of a-Al,O, and its agglomerate are shown in figs. 3c
and 3d respectively. It is clear from these TEM pictures that the a-A1203 formed by the combustion
process has nearly hexagonal platelet particles with
sizes ranging from 0.2 to 0.8 pm and the agglomerate

l_c;l_l_
io

50

LO
28 (deg)

30

Fig. 2. X-ray powder diffraction patterns of (a) a-A&O,, (b)

Y,AIS012, (c) 50 wt% t-ZrOz/A1203, (d) P-A1201 (Naz0,7.22
AI?O,), (e) MgA1204,and (f) LaAIO,.

sizes are greater than 1 urn. However, the average

agglomerate sizes of the various oxide materials determined by the particle size analysis (sedimentation method) are % 4 urn (table 1). A typical electron
diffraction of the as-prepared a-A120, is shown in
fig. 3e.
The Zr02/A1203 composite prepared by the combustion of an aluminium
nitrate-zirconyl
nitrateurea mixture has Zr02 in a metastable tetragonal
phase exclusively. The Zr02 crystallite size calculated form the X-ray line brodening
[ 141 (fig. 2c)
is z 175 A which is well below Garvies [ 15 ] critical
size for its transformation
into the monoclinic phase.
More interestingly,
it was observed that the metastable tetragonal phase of Zr02 is not only retained
but also the crystallite size did not increase even after
several heating and cooling cycles at 1180C. The
TEM micrograph of t-Zr02/A120,
(fig. 3f) shows a
uniform distribution
of intragranular
ZrOz particles
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MATERIALS LETTERS

July 1988

Fig. 3. SEM micrographs of (a) foamy macrostructure of a-A&O,, (b) surface of the foamy a-Al,O, and TEM micrographs of (c) a
of a-A1203, (d) an agglomerate of a-A1203, (e) an electron diffraction of a-A&Ox, and (f ) a-A1203 matrix with uniform
distribution of z 50 wt% t-ZrO,.
single particle

in the matrix of a-A1203. These t-ZrOz/A1203 powders are of much interest because of their potential
to yield martensitic
transformation
toughened alumina [16].
In order to confirm the attainment
of high temperatures
( x 1600C) during the combustion
of
metal nitrate-urea
mixtures, preparation
of ruby
powder (Cr 3+-doped a-Al,O,) was tried. It was gratifying that when a mixture containing
Al( N03)3+
430

9H20 (20 g), Cr(N03)3.6H20

(0.0148 g) and urea
(8 g) was used for the combustion at 500C a light
pink foamy powder was obtained. It was identified
to be ruby by its characteristic fluorescence spectra
[ 17 ] (fig. 4). In the excitation spectrum (fig. 4a) of
the fluorescence at 695 nm the two broad absorption
bands observed at 406 and 548 nm are assigned to
4A28-4T,9 and 4A29-4T2, transitions respectively [ 18 1.
The emission spectrum of ruby (fig. 4b) using an ex-

(b)

&/I

600

500
Wave

length

July 1988

MATERIALS LETTERS

Volume 6, number 11,12

LOO

trim)

300

_.J
700

635
Wave

L
,
I

630

66

Length tnm)

Fig. 4. Fluorescence spectra of ruby powder: (a) excitation spectrum and (b) emission spectrum.

citation wavelength of 550 nm shows a characteristic

band at 694 nm.

of the flame temperature by a pyrometer but also by

the formation of a-AlzOs, MgA&O, as well as ruby.
Formation of ruby, chromium-doped a-alumina
(Cr3+/Al,0,),
is known to take place only above
1300C.
The combustion process appears to be controlled
by the heating rate, stoichiometry and the mass of
the combustion mixture and the volume of the container. A heating rate of less than lOOC/min resulted in the formation of amorphous alumina. Fuelrich combustion mixtures yield products with carbon impurity. Compositions containing less than 5
g of aluminium nitrate in a container of a:300 ml
capacity (100 mm diameter and 50 mm height)
failed to ignite; however the same got ignited with a
container of z 100 ml capacity (50 mm diameter and
20 mm height) indicating that the mass-to-volume
ratio is critical for the exothermic gas-phase reaction
to occur in the combustion synthesis.

5. Conclusions
4. Mechanism
Redox reactions are usually exothermic in nature
and often lead to explosion if not controlled. The
combustion of aluminium nitrate-urea mixtures appears to undergo a self-propagating and non-explosive exothexmic reaction. Urea on heating is reported
[ 19,201 to decompose to biuret and ammonia initially and at higher temperatures to (HNCO), trimer. On the other hand, Al(N03)3*9H20 .[211 melts
on heating followed by dehydration and decomposition to amorphous alumina and oxides of nitrogen.
However, aluminium nitrate-urea mixtures when
heated are reported (221 to form Al(OH)(NOl)z
gel. Thus, during the combustion of aluminium nitrate-urea mixtures all these reactions appear to occur simultaneously forming a polymeric gel which
foams by the large amounts of gases produced. The
appearance of a flame may be attributed to the gasphase reactions in the foam of combustible gases like
ammonia and cyanic acid with oxides of nitrogen.
Ammonia-nitrogen oxide flames are known [ 231 to
give a flame having a temperature of z 2000 C. The
production of high temperatures ( s 1600C) during the combustion of aluminium nitrate-urea mixtures is confirmed not only by actual measurements

The combustion process described for the synthesis of tine particle u-alumina and related oxide materials has great potential in the preparation of
ceramic materials of technologicai and commercial
importance. Micron size u-alumina and related oxides are very important for preparing dense ceramics
and achieving a specific microstructure. Fine particle and homogeneous powders of ruby and NdYAG
are useful in producing ultra~ne lasers and new
phosphors for cathode ray tube screens respectively.

References
[I] W.M. Wheiidon, in: Modern materials, Vol. 2. ed. H.H.
Hausner (Academic Press, New York, 1968).

[ 21 B. Cockayne, in: Modem oxide materials, eds. B. Cockayne

and D.W. Jones (Academic Press, New

York, 1972) p. 1.

[ 31 N.B. Hannay. XXIVth International Congress of Pure and

Applied Chemistry, Vol. 3 ( 1973) p. 1.
[4]D.A.J.Rand,J.PowerSources4
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[ 5] A. Neville, High alumina cement (Wiley, New York, 1975).
[ 6 J G. Fisher, Am. Ceram. Sot. Bull. 63 ( 1984) 249.
[7 ] H. imai and T. Tagawa, J. Chem. SK Chem. Commun.
(1986) 52.
[ 8 1P. Vincentini, Ceramic powders. Preparation, consolidation and sintering (Elsevier, Amsterdam, 1983).

431

Volume 6, number 11,12

MATERIALS LETTERS

191 P. Rav~~dm~athaR and K.C. Fatit, Am. Gram. Sot. Buli.

66 ft987) 688.
[IO] P. Ravindranathan and KC. Patil, J. Mater. Sci. 22 (1987)
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[ 121 Powder Dif%action File, Inorganic Voi. PDfS - 10, Joint
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[ 131 G. Yamaguchi and K. Suzuki, Bull. Chem. Sot. Japan 41
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[ 141 H. Kiug and L. Alexander, X-ray diffraction procedures
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[15JR.C.Carvie,J.
Phys. Cbem. 69 (1965) 1238.
[ 161 D.W. Sproson and C.L. Messing, J. Am. Ceram. Sot. 67
(1984) C92.

432

July 1988

[ 17 ] Y. Hirai, T. Fukuda, Y. Kobayashi, H. Kuwahara, Y. Kido

and K. Kubota, Satid State Commun. 62 f 1987) 637.
f 18 1F. Varsanyi, D.L. Wood and A.L. Schawlow, Phys. Rev.
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[ZO] A.M. Wynne, J. Chem. Educ. 64 f 1987) 180.
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