Powder Technology 190 (2009) 95–98

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Powder Technology
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Elaboration of boehmite nano-powders by spray-pyrolysis

J.M.A. Caiut a,b, J. Dexpert-Ghys a,⁎, Y. Kihn a, M. Vérelst a, H. Dexpert a, S.J.L. Ribeiro b, Y. Messaddeq b
a
CEMES-CNRS, 29 rue Jeanne Marvig 31055 Toulouse, France
b
Photonic Materials Lab., Institute of Chemistry, UNESP Araraquara-SP, Brazil

A R T I C L E I N F O A B S T R A C T

Available online 1 May 2008 Boehmite (γ-AlOOH) synthesis have been investigated using a spray pyrolysis (SP) device starting from a
stable sol of Al-tri-sec-butoxide peptized by nitric acid. Free spherical particles from 100 to 500 nm have been
Keywords: elaborated. Particles sub-structure is made of nano-crystalline boehmite with very small average crystallite
Spray-pyrolysis size (one crystal cell along the b axis). The nano-crystalline boehmite synthesized by SP at low temperature
Nano-powders
(200 °C) is spontaneously dispersible in water without any surface treatment. Boehmite powder may be
Boehmite
Alumina
transformed to transition γ-alumina by heat post-treatment. Powders of sub-micrometric and spherical
Sol–gel γ-alumina particles may also be synthesized by SP at 700 °C.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction boehmite powder. The names “pseudoboehmite” or “nano crystalline

Spray pyrolysis (SP) is an aerosol process commonly used to form a
wide variety of materials in powder form including metals, metal
oxides, ceramics, superconductors, fullerenes. SP offers specific
advantages compared to other material processing techniques as
gas-to-particle conversion processes, liquid or solid-state processing
followed by milling. These advantages are a higher purity of the
produced powders, a better uniformity in chemical composition, a
narrower size distribution, a better regularity in shape and the
synthesis of multi-component materials. Another advantage is the
relative simplicity of the process which allows scale-up [1–4]. During
the past years, we have built in our group a pilot-scale SP apparatus for
the synthesis of sub-micrometric phosphor powders [5,6]. More
recently we concentrated on the obtention of nanometric powders [7].
In this paper we report on the synthesis of the γ-AlOOH (boehmite)
aluminium oxyhydroxide by the spray-pyrolysis of a precursor sol.
Boehmite is the most important precursor of the transition aluminas.
Transition aluminas are widely used in the industry of adsorbents and
catalysts [8,9]. γ-AlOOH is traditionally prepared by i) solid state
decomposition of gybsite, ii) precipitation from acidic or basic
aluminium aqueous solutions, iii) sol–gel procedures from aluminium
alcoholates. The third method allows the preparation of very pure
boehmite, although from more expensive chemicals. A very common
procedure was first described in [10,11]. It consists of aluminium
alkoxide hydrolysis followed by peptization to a clear sol, the gel
formation, and then the gel drying to get hydrated boehmite. Further
pyrolysis at higher temperature gives porous alumina. The control of
the drying conditions is necessary to control the properties of the
⁎ Corresponding author.
E-mail addresses: sidney@iq.unesp.br (J.M.A. Caiut), jdexpert@cemes.fr
(J. Dexpert-Ghys).
boehmite” are used in contrast to microcrystalline or well crystallized
boehmite. The nanocrystalline boehmites exhibit crystallite size less
than 10 nm, defects and numerous adsorbed water molecules: these
features strongly depend on the preparation conditions [12].
The γ-AlOOH powder synthesis described here is a droplet-to-
particle synthesis. As discussed in [13] for the case of titanium oxide, the
benefits of the aerosol route (i.e. the control of shape and size of the
particles) and the benefits of the alkoxide chemistry (i.e. the composi-
tional homogeneity) are combined in this procedure. The spray-
pyrolysis process may be decomposed in five steps: i) generation of a
spray from a liquid precursor by an appropriate droplet generator, ii)
spray transport by an air flow during which solvent evaporation occurs,
iii) thermolysis of the precipitated particles at higher temperature, iv)
intra-particulate sintering, v) finally, extraction of the particles from the
gas flow. We have proposed a global modeling of the first two steps with
the operating parameters employed in the pilot-scale set-up [14,15]. The
following step: i.e. the thermolysis of the precipitated particles, is very
dependant on the chemical system considered (each solid particle is in
fact a micro-reactor) and on the kinetics of the reactions in the micro-
reactor versus the total time of presence in the reactor. One advantage of
SP is to be flexible: the thermolysis may be conducted at any tem-
perature (from 200 to 1000 °C or more) so that low or high temperature
stable phases may be achieved in one step. Post synthesis annealing is
more often applied to the SP powders, either in conventional ovens or in
activated fluidized bed [16,17]. In the case under consideration here, the
sol–gel synthesis takes place at much lower temperature since the
conventional sol–gel synthesis of boehmite has been performed be-
tween 75 and 95 °C [10,11].
We describe in the following the operating conditions required to
obtain the nano-sized boehmite by SP, and some physico-chemical
characteristics of these nano-powders in particular their ability to be
dispersed in water. We also give the characteristics of the transition

0032-5910/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2008.04.054
96 J.M.A. Caiut et al. / Powder Technology 190 (2009) 95–98
aluminas synthesized in one step by SP at higher temperature or after
post-synthesis heat treatment.
2. Experimental
The precursor solution is prepared following the methodology
established by B. Yoldas [10]. Aluminum-tri-sec-butoxide 25.93 g/
0.1 mol is added to distilled water (300 mL) at 80 °C. After 2 h of
stirring, nitric acid is added as peptizing agent, up to 0.07 HNO3/Al3+
(molar). This sol is very stable: over months. Before processing, the sol
is diluted to the concentration 0.2 mol/L of Al3+, it is then poured into
the vessel over the piezoelectric pellet. The synthesis corresponds to
the following equation:
1AlðO–C4 H9 Þ3ðlÞ þ nH2 OðlÞ þ 0:07HNO3ðaqÞ →1AlOOH:0:75H2 OðSÞ
þ 3C4 H9 OHðgÞ þ 0:07H3 Oþ −
ðaqÞ þ 0:07NO3ðaqÞ þ ðn–2:82ÞH2 OðlÞ :
The laboratory scale SP device is schematized in Fig. 1. The spray is
generated by ultrasonic vibrations of a piezoelectric pellet (2.4 MHz)
immersed in the solution of precursor. The droplets are collected by an
air stream (0.3 m3/h) and drawn into a drying area maintained at 100–
120 °C, then a decomposition-densification area where the tempera-
ture may be adjusted up to 1200 °C (Tsynt in the following). Collection
of the dried powders is achieved by an electrostatic collector.
The residence time of the droplets in the hot zone is about 3–4 s.
The reactors are made of pyrex or of quartz depending on their
working temperature. The flow (vector gas + solvent and decomposi-
tion products vapors + solid particles) is then drawn in an electrostatic
precipitator consisting of two collection plates inside a quartz tube. A
5 mm metallic wire is maintained at 12 kV. The flow in the precipitator
is maintained at about 130 °C. Currently 500 mL of the precursor are
sprayed within 4 h, giving about 5 g of hydrated boehmite. Post-
synthesis heat treatments for one hour at Tpt are made in an oven
under air.
The powder morphologies are evidenced by electron microscopy
in the SEM mode in a field-emission scanning electron microscope
(Jeol JSM 6700F) or in the TEM mode with a Philips-CM12
transmission electron microscope. The obtained powders are char-
acterized by X-ray diffraction (XRD), on a Seifert XRD3000 diffract-
ometer. Crystallite sizes are calculated using the Scherrer equation
D = 0.9λ/(FWHM) cos θ with the full width at half maximum measured
in (2θ) an expressed in radians. Thermal analysis scans are recorded
with a TG-DTA/DSC Setaram, Labsys instrument, the powders put in
platinum vessels, under O2 atmosphere, with either 5 or 10 °C/min
heating rates. Nitrogen adsorption–desorption curves are measured
with a Belsorp-mini (BEL Japan Inc.) between 0 and 99 p/p0 at 77 K.
Pre-treatment was performed under vacuum during 24 h at 80 °C. The
Fig. 1. Scheme of the spray-pyrolysis set up.
Fig. 2. Thermogravimetric analysis of a sample γ-AlOOH obtained at Tsyn = 200 °C.
size distributions of as prepared boehmite dispersed in water are
determined by dynamic laser light scattering using a Brookhaven
apparatus with the BI-9000 particle sizing software.
3. Results
3.1. Thermal decomposition of the hydrated boehmite (Tsyn = 200 °C)
The thermal evolution of the boehmite samples obtained at Tsyn =
200 °C are analyzed by thermo-gravimetry (Fig. 2). An important
weight loss, corresponding to the dehydration — dehydroxylation of
the samples is observed from 30 to 450 °C, which could be separated
in two more or less distinct steps. The first step (30 to 200 °C) cor-
responds to the dehydration of physisorbed water molecules and of
part of the chemisorbed molecules, whereas the second step (200 to
450 °C) is due to the removal of chemisorbed molecules and to the
decomposition of boehmite into alumina. From 450 to 1000 °C, the
weight loss corresponds to the dehydroxylation of the surface of
alumina.
The dehydration-dehydroxylation processes can be expressed
following the formulas:
30−450˚C 450−1000˚C
AlOOH; nH2 O Y
E 1=2Al2 O3 ; mH2 O Y
E 1=2Al2 O3
The average formulation for our hydrated boehmites is then:
(Al1 − xEux)OOH, (1.2 ± 0.2)H2O. It must be noticed that the water
content may be slightly over-estimated because part of the weight
loss is due to the removal of residual nitrates (from the synthesis
mixture) and of adsorbed carbonates: these species are detected by
IR spectroscopy, but are not quantified.
3.2. X-ray diffraction
The X-ray diffractions recorded on powders elaborated at Tsyn =
200, 500 or 700 °C, respectively are displayed on Fig. 3. At Tsyn = 200 °C,
and at Tsyn = 500 °C the γ-AlOOH boehmite phase is synthesized. The
observed diffraction peaks positions agree well with the data reported
for micro-crystalline boehmite (JCPD no. 21-1307). There is a con-
siderable broadening of the diffraction peaks. The coherent lengths
(usually understood as the average crystallite sizes) evaluated with
the Scherrer formula following three directions are: 1.6 nm perpendi-
cular to the (020) plane, and 3 nm perpendicular to (120) and (031).
These are very weak values, characteristics of “nano-crystalline”
boehmite. For Tsyn = 500 °C, the peaks are slightly less broad, giving
coherent lengths of 2.6 nm (020), 4 nm(120) and 4 nm (031). The
 J.M.A. Caiut et al. / Powder Technology 190 (2009) 95–98 97

Fig. 3. X-ray diffraction of the SP samples, (a): Tsyn = 200 °C, (b): Tsyn = 500 °C, (c): Tsyn = 700 °C, (d): Tsyn = 200 °C, Tpt = 300 °C, (e): Tsyn = 200 °C, Tpt = 500 °C, (f): Tsyn = 200 °C, Tpt = 1000 °C.

Fig. 4. SEM images of particles. Left and centre: Tsyn = 200 °C, right: Tsyn = 200 °C + Tpt = 1000 °C.

powder synthesized at 700 °C gives a very badly resolved diffraction, residence time in the hot zone of the SP process is very short (few
with some peaks characteristic of the γ-alumina. seconds), so that the reactions cannot be completed.
The boehmites synthesized at 200 °C then submitted at post
treatments at various temperatures exhibit several phase transforma- 3.3. Electron microscopy
tions (Fig. 3 d to f). At 300 °C, γ-AlOOH transforms to a completely
amorphous state, then to γ-Al2O3 at 500 °C. Very sharp diffraction Some images of the powders obtained by scanning or by trans-
peaks of the α-Al2O3 corindon phase are observed at 1000 °C. The mission electron microscopy are gathered in Figs. 4 and 5.
boehmite powders prepared by spray-pyrolysis behave as it had been
reported previously for boehmite samples from other synthesis
methods. After 1 h post-treatment at 300 °C, the boehmite structure
has completely disappeared, whereas when the SP is performed at
500 °C, the boehmite structure is well defined. This is because the

Fig. 5. TEM images of particles. Left: Tsyn = 200 °C, right: Tsyn = 200 °C + Tpt = 1000 °C. Fig. 6. N2 adsorption – desorption curves.
98 J.M.A. Caiut et al. / Powder Technology 190 (2009) 95–98
Fig. 7. Distribution of hydrodynamic sizes for SP boehmite dispersed in water (pH = 7.0).
The boehmite obtained at Tsyn = 200 °C is made of spherical par-
ticles. Some particles have a diameter around 2 μm, whereas the major
part has a much smaller diameter (estimated from 500 nm to 100 nm).
At higher magnification, small platelet like elements around 100 nm
or less are observed on the sphere. After post treatment at 1000 °C, the
spherical morphology is well maintained, some inter-particulate
bridges are observed.
The transmission electron microscopy permits to probe the in-
ternal core of the particles. After synthesis, the particles are filled: this
is evidenced by the contrast between the center of the sphere and its
circumference. The image appears darker towards the center because
the electrons go through more matter. After post treatment at 1000 °C,
the powders are still made essentially of spherical filled particles. The
crystallization in the spheres is visible as smaller sub-particles (i.e. the
crystallites).
3.4. N2 sorption
Characteristic nitrogen absorption-desorption isotherms obtained
for SP-boehmite after treatment at 80 °C under vacuum are displayed
in Fig. 6. The surface area deduced from these curves is 180 m2/g.
3.5. Water dispersion of the boehmite
One very interesting property of the boehmite powders synthe-
sized by SP is that they are spontaneously dispersible in water at room
temperature and form very stable suspensions without re-agglomera-
tion and without any surface treatment. The size distribution of
particles in the stable sol was analysed by dynamic light scattering. A
representative histogram is displayed in Fig. 7. About 1% particles were
the isolated crystallites (around 5 nm diameter). 60% particles were
aggregates with about 30 nm in diameter, and the remaining 39%
particles had 60 to 80 nm size. It is worthy of note that the powders
obtained by slow drying the same sol do not form stable dispersion in
water.
4. Discussion and conclusion
The synthesis, with a spray pyrolysis device, of γ-AlOOH
(boehmite) has been investigated starting from a stable sol of Al-tri-
sec-butoxide peptized by nitric acid. Compared to the conventional
slow gel formation and gel drying, spray pyrolysis of the sol prevents
the long-range polymerization of the aluminate network. Well iso-
lated spherical particles are synthesized. Most particles exhibit size
from 100 to 500 nm. The particles sub-structures consist of nano-
crystalline boehmite with very small average crystallite size. The
crystal structure of γ-AlOOH first described in [18] is orthorhombic.
The unit cell consists of double layers of aluminium-centered dis-
torted octahedra AlO4(OH)2. The hydroxyls (OH groups) are at the
outer surface of the double layers and interact to hold the layers
together. The sequence of hydrogen-bonded layers expands following
the b axis. The crystallite size we have measured in the b crystal-
lographic direction is equivalent to only one cell: then a great number
of the OH are in fact at the surface of the crystals. As the OH groups are
adsorption sites for water molecules, this may explain why our nano-
crystalline boehmite is so much hydrated: AlOOH, (1.18 ± 0.22)H2O.
The water molecules at the surface of the nano crystals probably
stabilize the nano particules (or small aggregates of nano particles), to
form stable dispersion in water.
In summary, the spray pyrolysis of a sol is an easy process to
synthesize shape controlled spherical sub-micrometric particles of γ-
AlOOH (boehmite). Moreover these sub-micronic particles may be
easily destroyed in water to give a stable suspension of nanometric
(30–80 nm) particles. When performed at higher temperature, the
spray pyrolysis of the same sol gives sub-micrometric particles of
transition (γ-) alumina.
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