MICROWAVE-ASSISTED SYNTHESIS

AND CHARACTERIZATION
OF CaO NANOPARTICLES
ARUP ROY
*
and JAYANTA BHATTACHARYA
y
Department of Mining Engineering
Indian Institute of Technology
Kharagpur 721302, India
*aruproy08@gmail.com
y
jayantaism@gmail.com
Received 23 April 2010
Accepted 5 August 2010
Calcium oxide (CaO) is an important inorganic compound, which is used across various
industries as catalyst, toxic-waste remediation agent, adsorbent, etc. CaO nanoparticles were
obtained by the microwave irradiation technique, using CaNO
3

2
4H
2
O and NaOH as starting
materials. The formation of monocrystalline CaO nanoparticles was conrmed by the XRD
(X-ray diraction) and TEM (transmission electron microscopy) as well as by SAED (selected
area electron diraction) analysis. The structure of the CaO nanocrystal was found to be cubic
with particle size, 24 nm and surface area, 74 m
2
,g.
Keywords: Microwave technique; nanoparticles; CaO; transmission electron microscopy;
monocrystalline.
1. Introduction
Calcium oxide (CaO) is an exceptionally important
industrial compound, which is used as catalyst,
toxic-waste remediation agent, an additive in
refractory, in paint as well as for other fundamental
applications.
1
Ultrane metal oxide particles can be
used as bactericide and adsorbent. Particularly
CaO has also shown great promise as a destructive
adsorbent for toxic chemical agent.
2
Few literature are found on the preparation of
nano-CaO. There are mainly two methods on the
preparation of nano-CaO according to the litera-
ture. One is thermal decomposition.
3,4
The other is
solgel.
1
CaO nanoparticles can be obtained up to
about 14 nm size through solgel method, the cost
of which is very high. What is more, the process is
very complicated and time-consuming. So it is very
dicult to apply solgel method in industries.
Thermal decomposition method has some advan-
tages such as simple process, low cost, ease of
obtaining high purity product, etc. So it is a
promising and prospective method to be applied
into industry. In thermal decomposition method,
CaO is often obtained directly through calcining
CaCO
3
. High calcination temperature is needed. By
this process, it is very dicult to get nanoscale CaO,
but getting micrometer CaO (above 100 nm),
directly through calcining CaCO
3
is easily possible.
5
The microwave-assisted route is yet another
method for the synthesis of metal oxides and has

Correspondening author.
International Journal of Nanoscience
Vol. 10, No. 3 (2011) 413418
#.c World Scientic Publishing Company
DOI: 10.1142/S0219581X11008150
413
been gaining signicance in the synthesis of oxide
nanomaterials.
6,7
Microwaves have been used to
accelerate organic chemical reactions for some time,
because the method is generally fast, simple, energy-
ecient, and less time-consuming.
8,9
Unfortunately,
the exact nature of microwave interactions with
reactant during the synthesis of materials is some-
what unclear and speculative. However, energy
transfer from microwaves to the material is believed
tooccur either throughresonance or relaxation, which
results in rapid heating. Clark and Sutton
10
have
reviewed various aspects of microwave applications
reported in the literature. Several recent reports have
appeared which explain the microwave synthetic
route.
1118
Manymicrowave preparations reportedin
the literature have been made on the laboratory scale
of only a few grams.
1921
However, the use of higher
power levels for synthesis of ceramics for specialized
applications has also been reported.
22,23
The purpose of this study is to investigate a
simple and rapid synthesis method using calcium
nitrate and sodium hydroxide as starting materials
for the growth of the CaO nanoparticles. Advan-
tages of this method are as follows:
(a) The nanoparticles of CaO is formed by domestic
microwave oven.
(b) The preparation time is short.
(c) Less expensive method.
The characterization of the prepared metal oxides
was undertaken by employing structural (X-ray dif-
fraction (XRD) and spectroscopic (Fourier trans-
form infrared (FT-IR)) and surface morphological
(scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM)) techniques.
2. Experimental Part
2.1. Materials
CaNO
3

2
4H
2
O (Marck), sodiumhydroxide (Marck),
and deionized water were used; other reagents were
obtained from local supplies.
2.2. Preparation of CaO nanoparticles
In a typical procedure (Fig. 1), 0.5 M CaNO
3

2

4H
2
O and 0.7 M of NaOH were separately dissolved
in 50 mL deionized water and mixed to form 100 mL
mixture (solutions).
The mixture was stirred for 10 min at room
temperature and it turned into white gel. These
were then irradiated by microwave energy using
domestic microwave oven having frequency
2.45 GHz (maximum power 800 W) in ambient at-
mosphere for 10 min. After microwave processing,
the solution was allowed to cool to reach room
temperature, naturally. The resulting precipitate
was collected by vacuum ltration and washed with
deionized water and absolute ethanol, and dried in
vacuum at 80

C for 1 h.
2.3. Characterizations
The phase analysis and crystal structure of CaO
was studied by X-ray diractograms (XRD). The
XRD pattern was recorded using a diractometer of
Philips X-pert Pro X-ray diractometer (HRXRD)
with 0.1789 nm CoKc radiation. Particle sizes and
morphology were studied with a eld emission
scanning electron microscope (FESEM) of Carl
Zeiss model Supra-40 (with an accelerated voltage
1020 kV) and a high-resolution transmission elec-
tron microscope (HRTEM) of JEOL (JEM-2100),
with an operating voltage 200 kV. The average
compositional analysis for CaO was studied with
in situ EDS in conjunction with the FESEM ima-
ging of selective regions. In sample preparation for
HRTEM studies, a small portion of CaO was dis-
persed in acetone and sonicated for 30 min. Part of
this dispersion was dropped over a carbon lm
supported by a copper grid and dried in vacuum
before imaging. The IR spectra of thin pellets of
nanoparticles in the form of powder in a KBr matrix
were studied. A Nexus
TM
870 FT-IR (Thermo
Nicolet, USA) spectrophotometer equipped with a
deuterated triglycine sulfate thermoelectric cool
(DTGS-TEC) detector collected the data over a
range of 5004000 cm
1
.
2.4. Calculation of crystallite size
from X-ray diraction
Detailed knowledge of crystallite size, shape, and
strain in a nely divided powder often helps to
correlate many physical properties of a system
Fig. 1. Experimental procedure for synthesis of CaO
nanocrystals.
414 A. Roy & J. Bhattacharya
undergoing transformation in a solid-state reaction.
X-ray line broadening analysis provides a method of
nding bulk average size of coherently diracting
domains and r.m.s. strain. The average crystallite
size (D) from X-ray line broadening has been cal-
culated using the Scherrer equation.
24,25
The
instrumental broadening was corrected using quartz
as an internal standard:
D
0.9`
u
1,2
cos 0
.
where ` is the wavelength of the X-ray beam, u
1,2
is
the angular width at the half-maximum intensity,
and 0 is the Bragg angle.
2.5. Density evaluation from
X-ray data
The X-ray density of the samples has been com-
puted from the values of lattice parameters using
the formula
26
d 4
M
Na
3
.
where 4 represents the number of molecules in a
unit cell of a spinel lattice, M the molecular weight
of the sample, N the Avogadro's number, and a the
lattice parameter of the sample.
The lattice constant for the structure was
calculated using the equation
d
a
h
2
k
2
l
2

1,2
.
3. Results and Discussion
3.1. X-ray diraction studies
The XRD patterns of the synthesized calcium oxide
(CaO) are shown in Fig. 2.
The d-spacing values of the sample matched well
with the standard PDF database (JCPDS le 77-
2376). Unit cell parameters were obtained by least-
square renement of the powder XRD data. XRD
study revealed that the products are monophasic
cubic calcium oxide (CaO) with lattice constant
a =4.801 (Fm3m space group) having nanosized
particles; the values in the parenthesis indicate
respective Miller indices. The characteristic peaks
were higher in intensity and narrower in spectral
width, indicating that the products were of good
crystallinity. No peaks corresponding to impurities
were detected, showing that the nal are high-
quality CaO. The crystallite size, density, and
volume of the samples calculated from XRD data
are given in Table 1.
3.2. Microstructure studies
FESEM micrographs in Fig. 3 have nearly cubic
shapes of synthesized CaOnanoparticles with $30nm
average particle size on the cross sections.
These micrographs were taken from powder
coated with gold on a double-sided carbon tape.
Compositional analysis carried out with EDX ana-
lyzer (in conjunction with FESEM) showed no sig-
nicant impurity present in the sample (Fig. 4). The
observed peaks in Fig. 4 except Ca and O could
come from carbon tape.
Fig. 2. The XRD pattern of CaO nanoparticles immediately
after synthesis.
Table 1. A comparison of typical structural parameters in nanopowder and bulk CaO.
Parameter a Average size (D) (nm) Volume (V) (nm
3
) Density (,) (g/cm
3
) Surface area (m
2
/g)
Bulk CaO 4.808 0.11114 3.34
Synthesized CaO 4.801 24 0.11061 3.23 74.46
Microwave-Assisted Synthesis and Characterization of CaO Nanoparticles 415
Structural characterization through HRTEM
was rather a direct way that provides visual dem-
onstration to estimate particle size exactly. Figure 5
shows the typical HRTEM image of the synthesized
CaO nanocrystals.
Bright eld images of the sample indicate that
the sample was made of dispersive single-crystal
particles having cubic shapes. The selected area
electron diraction (SAED) pattern is shown in the
inset of Fig. 5. The SAED pattern recorded on
samples of nanoparticles indicates that they were
crystalline in nature. The SAED pattern had ve
reections (111), (200), (220), (311), and (222) at
0.2782 nm, 0.2403 nm, 0.1700 nm, 0.1451 nm, and
0.1389 nm, d
hkl
values in agreement to the XRD
values 0.2771 nm, 0.2400 nm, 0.1697 nm, 0.1447 nm,
and 0.1385 nm, respectively. The images showed an
abundance of particles whose size distribution was
given by the histogram shown in the inset of Fig. 6.
The histogram was obtained by analyzing several
Fig. 3. FESEM micrograph of synthesized CaO nanoparticles.
Fig. 4. EDX spectrum of the synthesized CaO particles
revealing the presence of calcium and oxygen.
Fig. 5. HRTEM micrographs of synthesized CaOH
2
nano-
particles with a selected area diraction pattern (SAED) in the
inset.
Fig. 6. Histogram showing the particle size distribution of
synthesized CaO nanoparticles.
416 A. Roy & J. Bhattacharya
frames of similar bright eld images using IMAGE J
software.
The particles have an average size of $25 nm,
which is in close agreement with an average D-value
$23 nm, determined from the XRD peak broad-
ening. Such particles (separated) show an average
surface area () of 74 m
2
,g.
3.3. Infrared spectroscopy studies
To verify chemical purity, CaO powders were ana-
lyzed by FTIR. The bands due to hydroxyl and
carbonate are distinctly displayed in the spectrum
(Fig. 7).
The strong band at 3643 cm
1
corresponds to the
OH bonds from the remaining hydroxide.
27
Bands
at 1417 cm
1
and 866 cm
1
correspond to the CO
bond. The wide and strong bands at around
427 cm
1
and 553 cm
1
correspond to the CaO
bonds (Table 2).
4. Conclusions
Nanostructured CaO with cubic morphology was
successfully produced from CaNO
3

2
and NaOH by
using a microwave radiation in ambient atmos-
phere. XRD, FESEM, EDX, TEM, SAED, and
FTIR analyses revealed the presence of face-centered
cubic structured CaOnanoparticles with 24 nmsizes.
It is a simple and ecient method to produce CaO
nanoparticles with regular shape, small size, narrow
size distribution, and high purity.
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