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Project Report
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Synthesis of BaTiO3 Nanoparticles for thermal sensing application

8th May, 2017 – 23rd June, 2017

Submitted By:-

Charu Tyagi
M.Sc. Chemistry
Amity University

Under the Supervision of:-

Dr. V. S. Pandey Dr. Sachin Tyagi

Sr. Scientist Scientist
CSIR-CSIO CSIR-CSIO

Central Scientific Instruments Organization

Sector-30-C, Chandigarh-160030
1. Introduction
a. Temperature sensors
Some of the most common type of sensors are temp. sensors or heat sensors.
They vary from simple ON/OFF mechanism to a highly-complicated
mechanism. Temperature sensors are of different types and all have different
characteristics depending on their properties. A type of temperature sensor
whose electrical resistance depends on their body temperature are called
resistance thermometer devices or RTDs. RTDs have high purity conducting
metals such as platinum, copper or nickel wound into a coil and whose electrical
resistance is a function of temperature. RTDs include metal element devices like
Platinum sensors of type Pt100 or Pt1000 and Ceramic Devices which are
commonly referred to as Thermistors.

b. Thermistors
The term thermistor is a contraction of words thermal and resistor. The name is
usually applied to metal-oxide sensors fabricated in a form of droplets, bars,
cylinders, rectangular flakes, and thick films. The term thermistor can be used to
refer to any RTD type sensor. However, it is usually for ceramic material
devices.The thermistors are constructed from ceramic materials such as oxides of
nickel, manganese or cobalt. Their main advantage is their speed of response to
any temp. change, accuracy and repeatability.
The ceramic thermistor devices can be divided into two categories PTC and
NTC. Components whose resistance increases as temp. increases have positive
temperature coefficient called PTC thermistors. PTC thermistors are typically
used for circuit protection applications rather than temp. sensing.And,
Components whose resistance decreases with increases in temp. have negative
temp. coefficient called NTC thermistors.

c. NTC thermistors
As the availability of integrated circuits is increasing, the demand for high
resolution temperature sensors is also increasing. The use of NTC thermistor
device gives a high resolution of +/- 0.1 to +/- 0.2 0 C in temperature sensing as
 compared to p-n junction temperature sensor.Suited for temperature sensing
applications over a range of -80 to +250 degree Celsius.

d. Semiconductor oxides
Metal oxide crystallizes in a variety of structures and bonding and can range
from ionic to semi-metallic to semiconductor(TiO2, MnO, NiO, FeO and CoO)
to metallic etc. The oxides of the metal in the middle of the periodic table (Sc to
Zn) comprise the semiconducting or metallic oxides. Semiconducting metal
oxides are the main component of a thermistor.For a higher resolution
thermistor, we need a suitable semiconducting metal oxide of Nano size to
achieve so.Solid materials may be divided into three categories conductors,
semi-conductors and insulators. The oxide semiconductors form a class of
materials in which conduction is electronic as opposed to ionic and which has a
lot common with intrinsic monocrystalline semiconductor such as Ge and Si.
The oxide semiconductors ae made of granules, each of which is a monocrystal
of a definitive structure, but the very large no. of grain boundaries must also play
an imp. part in semiconductor action. Conduction depends on physical
imperfections rather than on chemical impurities. While impurities can modify
the behaviour of an oxide semiconductor and a high order of chemical purity is
necessary in its constituents, such requirements are not nearly as stringent as in
monocrystalline materials. There are two forms of conduction and these are
recognized as resulting from excess of electrons or deficiency of electrons,
i.eholes. These correspond, not to acceptor and donor impurities but to two types
of lattice defects, Frenkel defects and Schottky defects. In a Frenkel defect there
is an extra ionized metal atom in the lattice which is not bound to an oxygen
atom and the electrons associated with this atom can take part in conduction. The
result is an excess or n-type semiconductor. In a Schottky defect there is a
positively ionized divalent metal atom missing from the lattice and to maintain
electrical neutrality two electrons must also have been removed. This results in a
deficit orp-type semiconductor. The n-type semiconductor corresponds to a
deficit of oxygen and the p-type to an excess of oxygen. This explains the
importance of the oxygen content of the atmosphere in which thermistors are
made and the importance of the heat treatment which produces the defects. This
qualitative summary is based on an excellent survey of the subject given by
 Goudet and Meuleau No quantitative theory appears to exist which can
adequately explain the behaviour of the oxide semiconductors

e. Ball mill
A ball mill is a type of grinder used to grind and blend materials for use in
mineral dressing processes, paints, pyrotechnics, ceramics and selective laser
sintering. It works on the principle of impact and attrition: size reduction is done
by impact as the balls drop from near the top of the shell. A ball mill consists of
a hollow cylindrical shell rotating about its axis. The axis of the shell may be
either horizontal or at a small angle to the horizontal. It is partially filled with
balls. The grinding media is the balls, which may be made of steel (chrome
steel), stainless steel, ceramic, or rubber. The inner surface of the cylindrical
shell is usually lined with an abrasion-resistant material such as manganese
steel or rubber. Less wear takes place in rubber lined mills. The length of the
mill is approximately equal to its diameter. Here the ball mill is used for
mechanical alloying for synthesis of BaTiO3 nano-powder from bulk of BaCO3
and TiO2 powders. Following is the picture of ball mill and jar used in the
process.

2. Experimental Procedure
An equimolar mixture of BaCO3 and TiO2 wasdry milled in agate jar of high-energy
planetary ball mill (PM100, RETSCH) in a continual regime with agate balls of
different sizes. The powders were milled with the ball to powder ratio (BPR) 10:1 at a
rotational speed of 200 rpm for different time intervals viz. 20 h (sample BT-1), 40 h
(sample BT-2) and 60 h (sample BT-3). The weight of the balls was 74.5g. Therefore,
the weight of reactants in grams should be 7.45 g. The formation of BaTiO3 from
BaCO3 and TiO2 follows the reaction:

xBaCO3 + xTiO2  BaTiO3 + CO2

where x=no. of moles.
Mol. Weight of BaCO3= 197.35
 Mol. Weight of TiO2=79.90
Therefore, (197.35+79.90)x =7.45g
x=7.45/277.25
x=0.02687
Therefore, moles=0.02687
Amount of BaCO3 taken = 0.02687 *197.35= 5.3068g
Amount of TiO2 taken =0.02687*79.9= 2.14g
Amount of BaTiO3 formed= 0.02687* 233.192= 6.266g
Samples were taken at 20 h, 40 h, and 60 h for XRD analysis and thermal sensing
applications. Samples were than annealed for 2 hours at 1000 0C.

All the glassware used for synthesis were made up of fine Borosil and includes glass
Petri plates, beakers, measuring cylinder. The other supporting apparatus include
spatula, centrifuge tubes(for storing the sample).

Table 2.2: List of instruments and apparatus used

Serial Apparatus Company
number
1 Weighing balance SHIMADZU AUW220D

2 Water bath ultrasonicate LOBA life

3 Ball mill RETSCH PM100

4 Spatula India

3. Characterization
The success or failure of any experiment is validated after the synthesized sample has
undergone through a series of characterization. Thus, a sample and an instrument are
the two fundamental requirements to carry out any experiment in nanotechnology. In
the work presented here, characterization techniques used to characterize the sample
prepared are described below. Phase identification of nanocrystalline samples was
done by X-ray diffraction (XRD) using Bruker AXS D8 diffractometer with Cu-Kα
radiation. The average crystallite size of the powder was measured by the X-ray line
broadening technique, employing Scherrer’s formula.

Unit cell is the smallest unit of a crystal, which, if repeated, could generate the whole
crystal. A crystal’s unit cell dimensions are defined by six numbers, the lengths of
three axes, a, b, c and the three inter-axial angles, alpha, beta, gamma as shown in
figure.

A crystal lattice is a 3D arrangement of unit cells. Space lattice is an imaginative grid

system in three dimensions in which every point (or node) has an environment that is
identical to that of any other point or node.
X-rays are electromagnetic waves having wavelength in the range of 0.1-100 A0 and
energies in the range of 120eV to 120keV. X-rays up to about 10keV (1-100 A0
wavelength) are classified as soft X-rays, and from about 10 to 120keV (0.1-1 A0) as
hard x-rays, due to their penetrating abilities. A beam of electrons I generated from
the hot tungsten filament and these electrons are accelerated towards the anode with a
high potential difference between the cathode ad anode (target). Anode is mainly Cu,
Mo, Al, Mg. after striking the anode the electrons generate the x-rays. While
monochromatic source is preferred, the x-rays beam actually consists of several
characteristics x-ray lines.
The periodic lattice found in crystalline structure may act as diffraction grating for
wave particles of electromagnetic radiation with wavelength of a similar order of
magnitude (1A0). The atomic planes of a crystal causes an incident beam of X-rays to
 interfere with one another as they come out from the crystal. This phenomenon is
called –ray diffraction.
XRD is a non-destructive technique. It is used to identify crystalline phases and
orientation. It helps to determine structural properties: strain, grain size, epitaxy,
phase composition, preferred orientation, order-disorder transformation, thermal
expansion and atomic arrangement. It can measure thickness thin films and
multilayers.
A single crystal will produce only one family of peaks in the diffraction pattern, while
a polycrystalline sample contain thousands of crystallites, therefore all possible
diffraction peaks should be observed. The main information procured from x-ray data
are: phase identification, volume fraction of the phases, crystallite size and strain. I
conclusion we can say that X-Ray is a very good technique for identification of the
sample.

4. Results and Discussions

The XRD data of samples show that the BaTiO3 nanoparticles has been formed. The
maximum peak intensity is at 32 which match with the JCPDS value. The size of
nanoparticles decreases as the milling time increases.

5. Conclusion
BaTiO3 nanoparticles were successfully synthesized by dry milling. BaTiO3 peak is
at 32 from XRD in all the three samples. The samples can be further used for thermal
sensing application.The particle size and crystallite size was observed to decrease
with increase in milling time.
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