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1.

INTRODUCTION

Nanotechnology is the science of particles under the size of 100 nm that has become a
great field of interest for many researchers in the past few years. Incredible development
in nanotechnology has paved ways for fundamentals in nano-biotechnology [1], quantum
dots [2], applied microbiology and many more fields. In recent years nanotechnology has
made its mark in various fields such as targeted drug delivery, chemical industry,
cosmetology and nano medicine.
Nanoparticles are found to have extremely small size reduced properties and high
surface to volume ratio that leads to both physical and chemical differences in their
properties as compared to macro particles with the same chemical configuration [3] [4]
[5] [11]. These particles also have many applications in different fields such as medical
imaging, nanocomposites, filters, drug delivery, and hyperthermia of tumors. [6] [7] [8]
[9]. Though nanoparticles are being produced by physical, chemical and biological
methodology for quite some time, researches are still trying to find out many new and
interesting ways to synthesis nanoparticles for varied particle application (Fig 1).

Fig 1 Methodology for synthesis of nanoparticles [10].

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Mechanical milling is a relatively new process of synthesis of nanoparticles. In this

methodology, a powder mixture of the desired nanoparticle to be synthesized is placed in
the ball mill and it is subjected to a very high-energy clashing from the balls. From this
approach of synthesis of nanoparticles, uniformly dispersed oxide particle formation is
relatively easier.
The ball milling system consists of a turn disc and two or four vials. The rotation of the
turn disc is in one direction while that of the vials are in the opposite direction. Thus due
to the rotation of the turn table and the vial in opposite direction to each other, a
centrifugal force is generated that are alternatively synchronized (Fig 2).

Fig 2 Motion of ball and powder mixture [12].

While performing the ball milling process, it is very important to keep in mind the
accurate ball-to-powder ratio (BPR). Generally, for small ball milling processes the BPR
denoted is 10:1 but for large ball milling the BPR can have a value 50:1 or 100:1. Along
with BPR some of the other factors to be kept in mind include RPM, filling volume and
different ball configuration as these parameters can very well effect the final synthesized
nanoparticle. In the recent years there have been many research conducted on various
metal oxides such as ZnO, TiO2, etc for their amazing properties that can be obtained by
manipulating their macro size dimension to a size into the nano size regime.
TiO2 is an extremely novel photo catalyst that can be used for the photo-degradation of
natural ecological contaminations [13] [14]. The photo generated electron-hole pair is a

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very important characteristic of TiO 2 as it is responsible for the initiation of a number of

reactions which eventually decompose the toxic organic molecules and thus reduce the
environmental contaminants [15] [16].
Just like TiO2, ZnO is another interesting photo catalyst which has drawn many interest of
many researchers. ZnO also has various unique optical and electrical properties same as
TiO2 [17] [18] [19]. ZnO nano particles these days are being researched in conducting
films, solar cells, cosmetology, photo catalysis and UV lasers [20]. But one of the most
important application of ZnO nano particles has been exploited as photo catalyst in the
treatment of environmental pollution especially in the field of water treatment [21] [22].
The application of both TiO2 and ZnO as photo catalyst has been made possible only due
to the feature of wide band gap of both materials [23].
In this paper, an effort has been made to synthesize TiO2 ZnO nanocomposites with the
help of physical method of ball milling for different percentage concentration and for
different milling time. The synthesized nanocomposites would be then characterized
using the X-Ray Diffraction Method.

2.

EXPERIMENTAL

2.1
SAMPLE PREPARATION
To prepare the sample for synthesis of nanoparticle through ball milling firstly 2.400
grams of TiO2 and 0.612 grams of ZnO were weighed to get 80-20% of TiO2 ZnO
composite and also 1.500 grams of TiO2 and 1.529 grams of ZnO were weighed to get a
50-50% of TiO2 ZnO composite and were put into two different vials respectively that
were made up of stainless steel with a capacity of 10 mL each. The vials also contained
six stainless steel balls and the diameter of each ball was 10 mm each. The vials were
then put in the SPEX 8000M Miller Mix of which the turn table rotation speed was 500
RPM and the BPR was 21:3. The milling time varied from 1 to 9 hours at room
temperature. After every 0.5 hours, 1 hour, 3 hours and 9 hours, 0.5 grams of the each 8020% and 50-50% of TiO2 ZnO sample were collected for further analysis.

TiO2 (mol

ZnO (mol

TiO2

%)

%)

(mol)

ZnO
(mol)

TiO2
(g)

ZnO
(g)

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80
50

20

0.03005

0.00751

2.400

50
0.01878
0.01878
1.500
Table 1: Measurement of TiO2 and ZnO required

0.612
1.529

2.2
INSTRUMENTATION AND CHARACTERIZATION
X Ray Diffraction can be used to look at single crystal or polycrystalline materials. A
beam of x-rays is sent into the sample and the way the beam is scattered by the atoms in
the path of the x-ray that is studied. The scattered x-rays constructively interfere with
each other. This interference can be understood using Braggs Law to determine various
characteristics of the crystal or polycrystalline material.
=2 sin
Where

is the wavelength,

is the inter planar spacing and

is the

diffracting angle. The synthesized sample was characterized by the X-ray diffraction
(XRD) with a Rigaku SmartLab (Fig 3) working at a voltage of 45 V and a current of 200
mA which utilized a mono chromatized Cu K radiation that had a wavelength of 1.5418
with a 2 value ranging from 10 to 80.

Fig 3: Rigaku SmartLab

3.

RESULTS AND DISCUSSION

Fig 4 shows the XRD peak obtained for 80-20% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 0.5 hours. The obtained XRD peaks indicate
that the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),

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Zincite (Z) and Anatase (A). The peaks obtained were at 17 (2,2,0), 10 (1,0,0) and 12
(2,1,2) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 1.22:12.5:86.

Fig 4: XRD of 80-20% TiO2 ZnO composite synthesized sample after 0.5 hours of ball
milling
Fig 5 shows the XRD peak obtained for 80-20% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 1 hour. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 26 (3,0,1), 7.9 (2,2,2) and 66
(1,0,1) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 4:13:5.

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Fig 5: XRD of 80-20% TiO2 ZnO composite synthesized sample after 1 hour of ball
milling
Fig 6 shows the XRD peak obtained for 80-20% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 3 hours. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 33 (1,1,1), 30 (0,2,1) and 28
(0,1,3) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 43:46:20.2.

Fig 6: XRD of 80-20% TiO2 ZnO composite synthesized sample after 3 hours of ball
milling

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Fig 7 shows the XRD peak obtained for 80-20% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 9 hours. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 49 (1,1,6), 50 (0,2,1) and 48
(0,0,4) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 18:62:20.

Fig 7: XRD of 80-20% TiO2 ZnO composite synthesized sample after 9 hours of ball
milling
Fig 8 shows the XRD peak obtained for 50-50% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 0.5 hours. The obtained XRD peaks indicate
that the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 10 (0,2,4), 11 (0,1,0) and 8
(1,1,2) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 0.4:44:54.

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Fig 8: XRD of 50-50% TiO2 ZnO composite synthesized sample after 0.5 hours of ball
milling
Fig 9 shows the XRD peak obtained for 50-50% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 1 hour. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 13 (0,0,2), 8 (1,1,0) and 9
(1,0,5) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 17:30:29.

Fig 9: XRD of 50-50% TiO2 ZnO composite synthesized sample after 1 hour of ball
milling

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Fig 10 shows the XRD peak obtained for 50-50% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 3 hours. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 5 (3,1,1), 8 (0,2,0) and 4
(1,3,2) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 3.5:18:3.

Fig 10: XRD of 50-50% TiO2 ZnO composite synthesized sample after 3 hours of ball
milling
Fig 11 shows the XRD peak obtained for 50-50% of TiO2 ZnO nanocomposite that was
synthesized after a ball milling process of 9 hours. The obtained XRD peaks indicate that
the particles synthesized are in the nano meter range. From this XRD pattern we can
identify the different phases of TiO2 ZnO composite nanoparticles such as Rutile (R),
Zincite (Z) and Anatase (A). The peaks obtained were at 13 (1,0,1), 3 (1,1,2) and 8
(0,3,1) respectively for the three obtained phases. The ration of R: Z: A obtained in this
synthesized sample was found to be 14.9:0.68:0.71.

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Fig 11: XRD of 50-50% TiO2 ZnO composite synthesized sample after 9 hours of ball
milling

4.

CONCLUSION

In this report, TiO2 ZnO nanocomposite has been successfully synthesized using the
physical technique of ball milling with percentage concentration of TiO2 and ZnO to be
80-20% and 50-50% respectively under the milling time 0.5 hours, 1 hour, 3 hours and 9
hours. The synthesized eight samples were then characterized using the XRD technique.
The results of XRD indicated that the sample synthesized were in the nano dimension.
Also the peaks were obtained for the phases such as Rutile, Zincite and Anatase which
had a tetrahedral, cubic and tetrahedral shape respectively.

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