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Trans. Phenom.

Nano Micro Scales, 3(2): 100-105, Summer – Autumn 2015


DOI: 10.7508/tpnms.2015.02.004

ORIGINAL RESEARCH PAPER .

Solution Combustion Preparation of Nano-Al2O3: Synthesis and


Characterization

M. Farahmandjou1, N. Golabiyan1,*
1
Department of Physics, Varamin Pishva Branch, Islamis Azad University, Varamin, I.R. Iran

ARTICLE INFO. Abstract

Article history The aluminum oxide materials are widely used in ceramics,
Received 18 January 2015 refractories and abrasives due to their hardness, chemical inertness,
Accepted 25 April 2015 high melting point, non-volatility and resistance to oxidation and
corrosion. The paper describes work done on synthesis of α-alumina
Keywords by using the simple, non-expensive solution combustion method using
Aluminum oxide nanoparticles glycine as fuel. Aluminum oxide (Al2O3) nanoparticles were
Combustion synthesized by aluminum nitrate 9-hydrate as precursor and glycine as
Glycine
fuel. The samples were characterized by high resolution transmission
Synthesis
electron microscopy (HRTEM), field effect scanning electron
microscopy (FESEM), X-ray diffraction (XRD) and electron
dispersive spectroscopy (EDS). As there are many forms of transition
aluminas produced during this process, x-ray diffraction (XRD)
technique was used to identify α-alumina. The diameter of sphere-like
as-prepared nanoparticles was about 10 nm as estimated by XRD
technique and direct HRTEM observation. The surface morphological
studies from SEM depicted the size of alumina decreases with
increasing annealing temperature. Absorbance peak of UV-Vis
spectrum showed the small bandgap energy of 2.65 ev and the
bandgap energy increased with increasing annealing temperature
because of reducing the size.

1. Introduction paper [1-3], it is promising as the electric-insulating


material used in the electronic devices.
Alumina (Al2O3) is one of the most widely used The importance of alumina as catalyst or catalytic
advanced ceramic materials. Alumina is one of support has also been widely recognized for many
representative electric-insulating materials. Since it chemical reactions [4-6]. The transparency of alumina
film and wide range of properties extend its
has high thermal conductivity and high chemical application in optics as well [7]. Aluminum oxide is
stability at high temperature compared to other the amphoteric oxide of aluminum with the chemical
electro-insulating materials such as glass, plastic, and formula Al2O3 for alpha phase namely corundum as
p shown in Figure 1. It is also commonly referred to as
*
Corresponding author alumina or aloxite in the mining, ceramic and
Email address: farahamndjou@iauvaramin.ac.ir materials science communities.

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Farahmandjou
u & Golabiyan / TPNMS 3 (22015) 100-105

There are various crysttal structures in the alumin na. Al(NO O3)3.9H2O waas completelyy dissolved inn 10 mL
AAmong the various crystal structuress, alumina th hat pure w m temperature and 10 g
water with stirrring at room
rreveals electrric insulation is of type. The -alumiina glycinee was added tto the solutioon under stirriing. After
hhas been conventionally
c y produced by annealiing that thee glycine wass completely solved in thee solution
aaluminum hy ydroxide deriv ved from aluuminum salts or the synnthesis tempeerature was inncreased to 10000C. The
mminerals at temperatures
t higher than 1000∘C [8-11]. pH waas maintaineed between 2 and 3 duuring the
TThe -alumin na can be allso produced d by fabricatiing synthe sis.
aamorphous alumina
a with methods usin ng liquid phaase The brown prodduct were evaaporated for 3 hours,
such as hydro othermal syntthesis [12], pllasma synthesis cooledd to room tem mperature annd finally caalcined at
[13], the soll-gel method d [14-17], freeeze drying of 6000C and 1000oC for 4 houurs to determ mine the
sulfate solutiions [18], con ntrolled hydrrolysis of meetal gammaa phase and aalpha phase reespectively [55-8].
aalkoxide [19 9], decompo osition of organo metalllic All analyses weere done for samples witthout any
ccompounds in n supercriticaal fluids and aerosol
a methoods washinng and more purification.. The specification of
[20] and preccipitation meethod [21], prrecipitation anda the sizze, structure and optical properties of the as-
sol-gel proccess and th hen annealin ng it at hiigh synthe sis and annnealed Al2O3 nanoparticlles were
ttemperature [22–24].
[ carriedd out. X-ray ddiffractometeer (XRD) was used to
These metthods need th he high temperatures, whiich fy the crystaalline phase and to estim
identify mate the
bbrings abou ut much consumption n of energ gy. crystallline size. Thee XRD patterrn were recorrded with
AAccordingly, low temperaature processees for produciing 2θ in tthe range of 4-85o with tyype X-Pert P Pro MPD,
-alumina arre desired fo or saving eneergy. Here, we w Cu-Kα : λ = 1.54 Å. Thee morpholoogy was
hhave prepareed Al2O3 nan noparticles by
b simple no on- charactterized by ffield emissioon scanning electron
eexpensive solution combu ustion method d using glyciine microsscopy (SEM) with type KY YKY-EM32000, 25 kV
aas fuel. and trransmission eelectron microscopy (TE EM) with
In this pap
per, novel alu umina ceramiic nanoparticlles type ZZeiss EM-9000, 80 kV. Thee optical propperties of
aare fabricatedd by using sy ynthesis comb bustion methhod absorpption were measured bby ultravioleet–visible
wwithout any purification
p a centrifugaation process to
and spectroophotometer (UV–Vis) w with optimaa SP-300
find new resuults and the sttructural, optiical and surfaace plus. A All the measuurements werre carried outt at room
mmorphologicaal characterizzation of thesse nanoparticlles temperrature.
aare done by using XRD, HRTEM, FE ESEM and UV-
vvisible analysses. 3. Ressult and disccussion

X-R
Rar diffractioon (XRD) att 40kV was used to
identify
fy crystallinee phases aand to estim mate the
crystallline sizes. X-ray diffraaction patternns of the
powdeer after heat ttreatment at11000oC were done for
crystall structure. Fiigure 1 show
ws the XRD ppattern of
aluminnum oxide at1000oC for 4 hours. α- A Al2O3 was
the onlly phase pressent for the ppowder calcinned above
1000oC C. The exhibiited picks corrrespond to tthe (012),
(104), (110), (113)), (024), (1116), (018), (3300) and
(119) of a rhombohedral struccture of α- Al2O3 is
identiffied using thee standard daata. The meaan size of
the orddered Al2O3 nanoparticlees has been eestimated
Fig. 1. Molecu
F ular structure of alpha alumin
na
from full width aat half maxximum (FWH HM) and
Debye -Sherrer form mula accordding to equaation the
follow
wing:
22. Experimeental detail
.
0.89
The γ-Al2O3 nanopartticles were synthesized
s by D (1)
synthesis coombustion using aluminum nitrate 9- B cos 
hhydrate as prrecursor and glycine
g as fueel. Firstly, 10
0g

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Farahmandjou & Golabiyan / TPNMS 3 (2015)100-105

where, 0.89 is the shape factor, λ is the x-ray processing removes all impurity from the alumina
wavelength, B is the line broadening at half the nanoparticles.
maximum intensity (FWHM) in radians, and θ is the
Bragg angle. The mean size of as-prepared Al2O3
nanoparticles was around between 10-25 nm from this (a)
Debye-Sherrer equation.
Figure 3a shows the SEM image of the as-prepared
spherical shape Al2O3 nanoparticles with diameter size
in the range of 35-80 nm and Figure 3b shows the
SEM image of the annealed Al2O3 with smallest
diameter of 10 nm at 600oC for 4 hours. Figure 4
shows the size measurement of 100 randomly selected
particles.
TEM images show a narrow size distribution.
Fitting it with a log normal curve, leads to a measured
mean diameter of 60 nm, with standard deviation of
about 10%.
(b)

Fig. 3. SEM images of the (a) as-prepared (b) annealed


Al2O3 nanoparticles at 6000C
Fig. 2. XRD pattern of Alumina at 1000 oC

SEM analysis was used for the morphological


study of nanoparticles of Al2O3 samples. With
increasing temperature the smallest particle size
decreases from 20 nm to 10 nm because of increasing
annealing temperature [12].
The transmission electron microscopic (TEM)
analysis was carried out to confirm the actual size of
the particles, their growth pattern and the distribution
of the crystallites.
Figure 5 shows the as-synthesized TEM image of
alumina prepared by wet synthesis. The as-
synthesized TEM image of sphere-like shaped of
Al2O3 nanoparticles prepared by precipitation route. Fig. 4. Particle diameter histogram of alumina nano
The average diameter of alumina nanoparticles was particles; the line plotted corresponds to fit using a log
about 10 nm. normal distribution
The principal novelty of the procedure developed
is that the alumina nanoparticles were analyzed In most of preparation methods reported by
without any purification and centrifugation by ethanol researchers [7, 9-18], they purify nanoparticles by
or water after preparation. In fact, heat treatment washing with water or ethanol. As you can see the
Al2O3 nanoparticles prepared by using this method,

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Farahmandjou & Golabiyan / TPNMS 3 (2015)100-105

have a regular distribution, uniform size and spherical


shape.

Fig. 5. TEM images of the as-prepared Al2O3 nanoparticles

Absorption in the near ultraviolet region arises from


electronic transitions associated within the sample.
UV–Vis absorption spectra of as-prepared and
annealed Al2O3 are shown in Figure 6. For as-
synthesized Al2O3 nanoparticles, the strong absorption
band at low wavelength near 471 nm correspond to
bandgap energy of 2.65 ev (figure 5a) and for
annealed Al2O3 at 600 oC and 1000oC the strong
absorption band at low wavelength near 400 nm and
402 nm correspond to 3.54 ev (figure 5b) and 3.43 ev
(figure 5c) respectively. The UV absorption ability of
Al2O3 is related with band gap energy.
The optical absorbance coefficient α of a metal
close to the band edge can be expressed by the
following equation:

α = A(hν-Eg)n/ hν (2)

Where α is the absorption coefficient, Eg is the


absorption band gap, A is constant, n depends on the
nature of the transitions, n may have values ½, 2, 3/2 Fig. 6. UV–Vis absorption spectra of Al2O3 nanoparticles
and 3 corresponding to allowed direct, allowed
indirect, forbidden direct and forbidden indirect 4. Conclusion
transitions respectively. In this case n=1/2 for direct
allowed transition [11]. Alumina ceramic nanoparticles were successfully
The absorption spectra of TiO2 nanoparticles are prepared using aluminum nitrate and glycine. XRD
shown in Figure 6a. The absorption band edges were spectrum shows rhombohedral (hexagonal) structure
estimated around 351 and 362 nm (about 3.54 and of α-Al2O3 annealed at 1000oC. From SEM images, it
3.43eV).
is clear that with increasing temperature the mean size
The band gap energy can be determined by
extrapolation to the zero coefficients, which is of alumina decreases from 35 nm to 80 nm. TEM
calculated from the above equation. The intercept of image exhibits that the size of as-synthesized Al2O3
the tangent to the plot (αhν)2 versus hν in Figure 6b decreases to 10 nm. The UV–vis absorption show the
gives a good approxim-ation of the band gap energy small band gap is found to be 2.65 eV and the
for this direct band gap material.

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Farahmandjou & Golabiyan / TPNMS 3 (2015)100-105

bandgap energy increase with increasing annealing [9] I. N. Bhattacharya, P. K. Gochhayat, P. S.


temperature because of reducing the size. Mukherjee, S. Paul, P. K. Mitra, Thermal
decomposition of precipitated low bulk density
basic aluminum sulfate, Materials Chemistry
ACKNOWLEDGMENTS and Physics 8(1) (2004) 32–40.
[10] E. Ryshkewitch, Oxide Ceramics, Academic
The authors are thankful for the financial support of Press 1960.
varamin pishva branch at Islamic Azad University for [11] J. S. Reed, Principles of Ceramics Processing,
analysis and the discussions on the results. Wiley-Interscience, New York, NY, USA, 2nd
edition, 1995.
[12] W.L. Suchanek, Hydrothermal synthesis of
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