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Structural and Phase transition of Aluminium oxide nano powder

Technical Report · December 2015

DOI: 10.1080/01411594.2015.10726281

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 Phase Transitions
A Multinational Journal

ISSN: 0141-1594 (Print) 1029-0338 (Online) Journal homepage: http://www.tandfonline.com/loi/gpht20

Structural and phase transition of α-Al2O3 powders

obtained by co-precipitation method

R. Bharthasaradhi & L.C. Nehru

To cite this article: R. Bharthasaradhi & L.C. Nehru (2016) Structural and phase transition of
α-Al2O3 powders obtained by co-precipitation method, Phase Transitions, 89:1, 77-83, DOI:
10.1080/01411594.2015.1072628

To link to this article: http://dx.doi.org/10.1080/01411594.2015.1072628

Published online: 16 Dec 2015.

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 Phase Transitions, 2016
Vol. 89, No. 1, 7783, http://dx.doi.org/10.1080/01411594.2015.1072628

Structural and phase transition of a-Al2O3 powders obtained

by co-precipitation method
R. Bharthasaradhi and L.C. Nehru*

Department of Medical Physics, School of Physics, Bharathidasan University, Tiruchirappalli,

India

(Received 20 March 2015; accepted 10 July 2015)

Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

Aluminium oxide has been synthesized by co-precipitation technique at different

annealing temperature. Powder XRD confirms the formation

of a-Al2O3 with


rhombohedral crystal structure having lattice constant a D 4.76 A and b D 12.99 A by
the Scherer formula, the average crystallite size is estimated to be 66 nm. The
scanning electron microscope results expose the fact that the a-Al2O3 nanomaterials
are seemingly porous in nature and highly agglomerated. Chemical composition of
aluminium oxide is confirmed by energy dispersive spectroscopy. The molecular
functional group is confirmed by FTIR. Optical absorption of a-Al2O3 has been
studied in the UVvis region and its direct band gap is estimated to be 5.97 eV. This
study involves the structural and phase transition of Al2O3 and also indicates that
a-Al2O3 has considerable properties, deserving further investigation for the energetic
materials with excellent properties for the possibility of using thin-layer a-Al2O3 as a
thermo luminescence material.
Keywords: Al2O3; phase transition; co-precipitation method

1. Introduction
Recently, synthesis of nanostructured oxide materials has attracted considerable attention.
The metal oxides are extremely important technological material used in electronic and
photonic device and as catalyst in chemical industries. And in recent days, the research is
more focused on the synthesis of Al2O3 due to their application in advanced technologies.
[1] Latterly, alumina nanoparticles are receiving considerable interest as a possible
approach to enhance the energy release from energetic materials.
There are 15 distinct crystallography phases, such as gamma, delta, theta and alpha,
which could be obtained as the function of annealing temperature. Among them, alpha
alumina phase is the most thermodynamically stable phase due to their properties, such as
high hardness, high stability, high insulation and transparency.[2] The polycrystalline
a-Al2O3 is extensively used for ceramic application.[3] a-Al2O3, in the form of single
crystals, powders and thin layers on substrates are considered to be good thermolumin-
scence phosphors due to their high radiation sensitivity, simple glow curve, low back-
ground and dose threshold, low fading in the dark, good reproducibility, simple emission
spectrum, wide dose range and relatively low atomic number.[4] Aluminium oxide nano-
particles can be prepared by various methods, such as mechanical milling,[1] vapor phase
reaction,[2] co-precipitation,[3] sol-gel,[4] hydrothermal,[5] combustion method[6] and
homogeneous precipitation.[7] Each of this technique has its own merits and demerits.

*Corresponding author. Email: lcnehru@bdu.ac.in

Ó 2015 Taylor & Francis

 78 R. Bharthasaradhi and L.C. Nehru

In this way, an aluminium oxide nanoparticle is prepared using a co-precipitation

technique and the main object of this study is to find out the transition of Al2O3 nanopow-
ders prepared by means of the co-precipitation method; also structural characteristics of
transformed a-Al2O3 were studied. Here, the a-Al2O3 [1] nanopowders obtained were
annealed at 1000
C, 1100
C, 1200
C, 1300
C and characterized using XRD, scanning
electron microscope (SEM), energy dispersive spectroscopy (EDS), FTIR, and UV-vis
spectroscopy. For technological application, monitoring of transition from x to a phase
[8] is a very crucial factor. This study aims at finding out the suitable high temperature
for the Al2O3 to undergo variety of transition during its various phases, thus providing the
most stable a-Al2O3 structure.

2. Materials and methods

Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

The chemicals used for material preparation, such as aluminium chloride (AlCl3) and
ammonia were of analytical grade. Aqueous aluminium chloride was co-precipitated by
using ammonium hydroxide.[9] The co-precipitated aqueous solution was dissolved in
each case by adding this salt with distilled water. The mixed co-precipitated chloride
solution containing aluminium was slowly added to 5 ml ammonia solution. After obtain-
ing a homogeneous solution, the reagents were mixed using magnetic stirring. The co-
precipitate mixture was separated from the reaction mixture and washed several times
with distilled water and filtered. The obtained powders were dried at 100
C using hot
plate and it was subsequently annealed at various temperatures (1000
C, 1100
C,
1200
C and 1300
C) using muffle furnace.

3. Characterizations
The different phase of crystalline nature [5] (g-Al2O3, x-Al2O3 and a-Al2O3) [10] present
in the nanopowders after precipitation annealed at various temperatures (1000
C,
1100
C, 1200
C and 1300
C) were identified by powder X-ray diffraction using Cu K a
radiation


employing a scanning rate of 0.02 s¡1 in the angle ðuÞ of 10
80
with λ D 1.54
A. FTIR studies were carried out with JASCO 460 PLUS FTIR spectrometer from 400 to
4000 cm¡1 to identify the various functional groups present in the material. Morphologies
of the samples were investigated by SEM analysis using Hitachi SEM400. The chemical
compositions were analyzed through EDS. UVvis absorption spectrum of aluminium
oxide was recorded at room temperature between 190 and 600 nm using a Perkinelmer
UVvis spectrophotometer.

4. Results and discussion

4.1. Structural characterization
Structural characterization of synthesized samples after precipitation was carried out to
study the evolution of the required phase (a-Al2O3) with respect to the annealed tempera-
ture (1300
C).[11] Figure 1 shows the recorded powder X-diffraction pattern with
intense peak of a-Al2O3 at 43.27
and 57.42
, all the other peaks were identical and
matched with JCPDS 00-010-173. The major peaks located at 2u D 43.27
is indexed as
(113) which can be readily ascribed
to the characteristic


peaks of the rhombohedral struc-
ture with lattice constant a D 4.76 A and b D 12.99A.
 Phase Transitions 79

(1 0 4)

(1 1 6)
(1 1 3)
0
d = 1300 C
0
c = 1200 C
0
b = 1100 C
0
a = 1000 C

(0 1 2)

(3 0 0)
(0 2 4)
(1 1 0)
Intensity (counts)

(2 1 4)

(1 0 10 )
(1 2 2)
d

a
Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

20 25 30 35 40 45 50 55 60 65 70 75 80
2 θ (Degrees)

Figure 1. XRD pattern of aluminium oxide.

The Scherer equation,

 
Kλ
DD ;
bCosu

where D is the crystallite size, λ is the wave length of X-ray beam, K is the constant
(0.94), b is the peak width at half maximum intensity and u is the peak position used to
derive the crystallite size and is estimated to be 66 nm.
a-Al2O3 heated at 1300
C shows a highly crystalline nature than the other three
heated samples (1000
C, 1100
C and 1200
C) which are found to be of amorphous
nature. The characteristics of nano-alumina particles have been highly variant; this is pri-
marily due to the aging process as well as the phase transformation effect of thermal treat-
ment of the feedstock powders so that the morphologies and crystallite size are
distinctively noticeable. The conversion of corundum structure depends on the tempera-
ture and the time of thermal treatment. Total conversion occurs on heating above
1300
C.
The FTIR spectrum of a-Al2O3 nanoparticle is shown in Figure 2. The higher energy
region peaks 3457 cm¡1 are assigned to OH stretching of a-Al2O3 nanoparticles. This
stretching of OH occurs only after 1230
C leading to the formation of a-Al2O3 by the
solid state thermally driven transformations from hydroxyl group of aluminium oxide.
When the annealing temperature is below 1230
C, the possibility of dehydration level of
this hydroxyl group is less leading to the formation of g-Al2O3.[8] This in turn strength-
ens the Al2O3, thus forming a-Al2O3. The degree of transition to the corundum structure
depends on the time and the temperature of annealing treatment. Also a strong alkyl
halide was observed at 593 and 445 cm¡1 upon verification with the present database and
the spectrum matches with a-Al2O3.
 80 R. Bharthasaradhi and L.C. Nehru

o
1300 C
1635

2919

Transmittance (%)
3444

512

446
3900 3600 3300 3000 2700 2400 2100 1800 1500 1200 900 600
Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

-1
W ave number (cm )

Figure 2. FTIR spectrum of aluminium oxide.

4.2 Morphological and elemental analysis

The morphology and structure of the prepared particle was studied using scanning elec-
tron microscope. As the sample is to be well crystallized in 1300
C, SEM images are
recorded and shown in Figure 3. It shows highly porous with highly agglomerate size.
The chemical compositions of the present aluminium oxide sample after annealing were
determined by EDS and shown in Figure 4 with reference peak at 0 Kev. Spectrum study
reveals the presence of aluminium and oxygen elements with 38 and 62 atomic weight
percentages without impurities and it confirms the stoichiometry of aluminium oxide
nanomaterials synthesized by the co-precipitation method.

Figure 3. SEM image of aluminium oxide.

 Phase Transitions 81
Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

Figure 4. EDS spectrum of aluminium oxide.

4.3. Optical studies

The optical absorption coefficient (a) of the material was calculated from the absorbance
(A) using the relation,

a D 2:303logðAÞ=d;

where d is the thickness of the sample.

Initially, a graph was drawn between log (ahn) and log (hn) for the samples and is
shown in Figure 5. The graph is almost linear and hence the transition is identified to be
direct in nature. The optical band gap was determined by using the Tauc formula

ðahyÞ2 D Aðhy ¡ EgÞn;

350

300

250
Absorbance ( a.u )

200

150

100

50

200 300 400 500 600 700 800

wavelength (nm)

Figure 5. UVvis absorption spectrum of aluminium oxide.

 82 R. Bharthasaradhi and L.C. Nehru

o
1300 C
250000

200000

150000

2
αhν)
(α 100000

50000

5 .9 7 e V
0
5 .0 5 .2 5 .4 5 .6 5 .8 6 .0 6 .2
P h o to n E n erg y (eV )

Figure 6. Band gap of aluminium oxide.

Downloaded by [Bhartha Saradhi] at 20:52 16 December 2015

where a is the absorption co-efficient corresponding absorption edge (nm), hy is the pho-
ton energy and λ is the constant proportionality, respectively.
The plot of (ahy)2 versus photon energy for direct allowed transition in the intercept
at a D 0 gives the value of the optical absorption edge. Hence, the variation of (ahn)2 ver-
sus hn in the fundamental absorption region is plotted in Figure 6 and the optical band gap
is evaluated by the extrapolation of the linear part. Thus, the band gap is estimated to be
5.67 eV.

5. Discussion and conclusion

The aluminium oxide nanopowder was prepared successfully by the co-precipitation
technique. The main objective of achieving the most stabilized state of a-Al2O3 has
been achieved at 1300
C, other annealing temperatures were found to produce un-
stabilized states of a-Al2O3. In particular, Al2O3 annealed at 1300
C shows a better
crystalline form than the other three annealed samples (1000
C, 1100
C and 1200


C). The crystallite size of synthesized nanopowder annealed for 2 hour at 1300
C
was evaluated by using the Scherer formula and is estimated to be 66 nm. XRD
results show the complete absence of impurities in the nanopowder material; this is
due to partial transformations of these intermediate phases, like u and d. The pres-
ence of high energy bands in the FT-IR spectrum dehydrates the OH group at
1300
C causing stretches and strengthens the formation of nanoparticles; thereby
stable a-Al2O3 is formed using this method. The SEM image shows that the mor-
phology of a-Al2O3 is highly porous with highly agglomerate size, and it could be
concluded that the collapse of porous nature occurs in low temperature (1000
C,
1100
C and 1200
C), when compared with the stabilized structure. The presence
of Al and O elements in the sample was confirmed by the EDS spectrum. Linear
optical properties from absorption spectra estimated the Tauc’s plot band gap
value is found to be 5.97 eV. This study could be further enhanced by analyzing the
growth of crystals when subjected to various temperatures and mainly it could be
analyzed when the aluminium oxide material achieves its stabilized state.

Disclosure statement
No potential conflict of interest was reported by the authors.
 Phase Transitions 83

Funding
One of the Authors Mr. R. Bharthasaradhi gratefully acknowledge the financial support of DST-
PURSE for carry out this Research [4181/E18/2013].

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