CHAPTER-2

SAMPLE
PREPARATION
AND
TECHNIQUES
Chapter 2 Sample preparation and experimental techniques

Chapter 2

SAMPLE PREPARATION AND EXPERIMENTAL TECHNIQUES

2.1 Sample Preparation

2.1.1 Introduction:

Ceramic Materials are one of the major groups in material science because of their direct
and indirect applications in day to day life. Hence the synthesis of new ceramic powders is
of great importance in the progress of material science. The processing method for
preparing a material is broadly guided by two factors. One is the cost of preparation and
another is its end application. Electro-ceramic materials are advanced materials whose
properties and applications depend on the close control of structure, composition and
ceramic material, which can be achieved through specific synthesis process. The dynamics
of quality optimization and cost effectiveness have resulted in a variety of improved
methods in the ceramic industry. In general, the preparation of ultra fine, high purity and
homogeneous ceramic powders are required for multifunctional applications. Once the
ceramic material is prepared, the immediate step follows is the characterization to the test
the suitability of the material for specific application. Proper characterization of ceramic
materials includes various experimental techniques to probe the different aspects like
structure, surface morphology, electrical, magnetic properties etc.

2.1.2 General methods of preparing ceramic samples:

Ferroelectrics in general and multiferroics in particular can be obtained in many forms like
single crystals, ceramics (an assembly of small single crystals oriented with respect to each
other in a more or less completely random way) and thin films [195-197]. While single
crystals and thin films require highly sophisticated procedure, the ceramics can be
fabricated more easily, and in a cost effective way [196-199]. Moreover, ceramics have
additional structural and micro-structural features, which can be exploited in designing the
electro-ceramic materials for particular device application. Ceramic processing is a
sequence of operations like mixing, calcination, sintering etc. that intentionally and
systematically changes the chemical and physical properties of materials. The properties of
each stage are a function of the characteristics of the system. It is very important to identify

31
Chapter 2 Sample preparation and experimental techniques

different characteristics of the system, and also to understand the effect of processing
variables on the evolution of these characteristics. There are mainly two approaches for
synthesis. One is the mechanical method and the other is the chemical method.

1. Mechanical methods:
(i) Mixed oxide method or solid-state reaction method - Mixed oxide method or
solid-state reaction route is one of the most widely used methods for the
preparation of polycrystalline compounds. It is necessary to heat the precursors
to high temperature (to about 1000oC) as they do not react at room temperature.
The factors on which the feasibility and rate of a solid state reaction depends on
are reaction condition, surface area of the solids, structural properties of the
reactants, their reactivity.
(ii) High energy ball milling – With the help of an automatic or semiautomatic
machine it is preferable to perform the grinding and polishing procedures. The
structure of each and every ceramic product has been specifically adjusted to
exhibit required properties, and hence unique behavior is exhibited by each
material.

2. Chemical Methods:
(i) Co-precipitation method – The required compound is dissolved from the
starting mineral, thus allowing impurities to be filtered out. Precipitation from
solution gives an intermediate compound and by heating it the desired
compound is formed. This method is adopted because (i) it is quite simple and
fast, (ii) size and composition of the particle can be controlled easily (iii)
achieving overall homogeneity.
(ii) Sol-gel process – In sol-gel preparation, a solution of the appropriate precursors
(metal salts or metal organic compounds) is formed first. Then this solution is
converted into gel after hydrolysis and condensing. Drying and calcination of
the gel gives an oxide product.
(iii) Hydrothermal synthesis – The mechanism of hydrothermal reactions follows a
liquid nucleation model. Principles consist of theories of chemical equilibrium,

32
Chapter 2 Sample preparation and experimental techniques

chemical kinetics and thermo-dynamical properties of aqueous systems under

hydrothermal conditions.
2.1.3 Solid state reaction method /Mixed oxide method

In the present study solid state reaction technique has been employed for the
preparation of polycrystalline samples. This is a conventional method in which oxides
and carbonates are used. These chemicals have to meet a certain application dependent
specification with respect to their purity and grain distribution. The flow chart of the
mixed oxide method is given in Fig. 2.1.

Fig. 2.1: Flow chart for the preparation of ceramic samples by a solid state reaction
technique.
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Chapter 2 Sample preparation and experimental techniques

The general methods for processing of the materials consist of the following steps:

 Raw materials

Raw materials are selected on the basis of purity and particle size, which are required for
attainment of chemical equilibrium, particularly for the formation of solid solution.
Impurities can affect the reactivity as well as electrical properties of the mixed ceramics.
When raw materials have volatile ingredients or impurities, the ignition losses must be
taken into account.

 Weighing and mixing

Weighing exact amount of the constituent materials of the sample with due allowance for
impurity and moisture content is the first step in preparation of the ceramic sample. Often,
to reduce the moisture content the raw materials are kept in oven at 150oC for several hours
before they are weighed. The constituents must be taken in proper stoichiometry. The
required amount of different chemicals (i.e., metallic oxides or carbonates) needed for the
synthesis of a given amount of ceramics is calculated as follows:

Let M be the molecular weight of the desired ceramics and m be the amount (in gram) of
prepared material. Ma is the molecular weight of ath metallic oxides or carbonates used in
the fabrication of ceramics in the Z fraction of the ‘a’ metallic ion are present. Then the
weight required for ath metallic oxides or carbonates is given by ma where

M a mZ
ma = M

The next step is mixing, eliminating aggregates and reducing the particle size. The
constituents of a ceramic body need to be intimately mixed so that the neighboring particles
can inter-diffuse, which is essential for compound formation during calcination. So the
mixing process makes a homogeneous mixture of the precursors. The physical properties of
the ceramics are greatly suffered, if there is a lack of homogeneity in the ceramics. For
better homogeneity proper mixing is necessary in dry medium followed by wet mixing (i.e.,
in solvent like methanol) for sufficient time. Then the wet mixture is kept in air for
sometimes to dry by slow evaporation.

34
Chapter 2 Sample preparation and experimental techniques

 Calcination

Calcination process is an endothermic decomposition reaction in which an oxy-salt, such as

carbonates or hydroxides, decomposes into a solid product (oxide) and releasing the
gaseous products. During this decomposition reaction the particle size, its distribution,
extent of agglomeration, porosity and morphology are usually established. Calcination
causes the precursors to interact by inter-diffusion of their ions. Calcination is often the
final step in the production of high-purity ceramic powders. During calcination surface
absorbs water vapors, any volatile impurities and carbon dioxide from carbonates are
removed and thermo-chemical reaction among the constituent oxides takes place to form
the desired compounds. To achieve homogeneous single phase compound double
calcination step is often adopted.

 Grinding and pelletization

Grinding can be accomplished by any suitable means (e.g., agate mortar and pestle, ball
milling etc.). It helps to mix the constituent materials for ceramic preparation and also
homogenize the compositional variation, which may arise during calcination. If the
grinding is coarser the ceramics can have large inter-granular voids and low density. If
grinding is too fine, the colloidal properties may interfere with subsequent forming
operations. The calcined powders are again ground to very fine powder and mixed with
polyvinyl alcohol (PVA) which is used as a binder to reduce brittleness of the pellets, and
then pressed (using a hydraulic press) into desired shapes. The binder is used for better
compactness among the granules of the materials. For the conventional method of cold
pressing, the mixture of finely ground calcined powder with PVA is pressed using a dye-
punch by a hydraulic press. The samples are usually circular, rectangular or cylindrical in
shape as desired.

 Sintering

It is often difficult to obtain dense, pore-free ceramic element. Sintering is a process in

which fine grains or powders are converted to dense products after heating to an
appropriate temperature (below the melting point of the materials). After sintering the inter-
granular voids vanish and due to shrinkage of the whole system. Initially a decrease in the

35
Chapter 2 Sample preparation and experimental techniques

volume fraction of pores takes place due to the process of crystalline growth and
rearrangement of grains in the powder. At the next stage, pores are completely eliminated
by the approach of grain centers and increase of the area of contact between the grains, due
to mass transport from the inter-grain contacts towards the pores. The binder present in the
sample is burnt out during the sintering process.

 Electroding

To study electrical properties, the sintered samples are electroded using a suitable
conducting material. Silver, gold, graphite, platinum, etc., are normally used as electrode
materials after taking care of the following factors:

 It should adhere to the sample,

 It should have almost zero contact resistance and
 It can be pasted in the form of a thin layer/film.

Electrode adherence is critical on the smooth ceramic pellet. There should not be any gap
between electrode and the flat faces of the pellet; otherwise, these gaps will affect the
electrical properties of the sample. Hence, the sintered pellets are polished with fine emery
paper to make both the faces flat and parallel. These pellets are electroded with high-purity
electrode materials for electrical characterization.

2.1.3 (A) Preparation of the ceramics

The polycrystalline samples of (Bi1-xAx)(Fe1-xNbx)O3 where A=Li, Na and K; and x=0.0,

0.1, 0.2, 0.3, 0.4 and 0.5 were prepared by a solid-state reaction method using AR grade
(>99%) precursors such as Bi2O3, Fe2O3, Nb2O5 Li2CO3, Na2CO3 and K2CO3 (all from M/s
LOBA Chemie Pvt.Ltd., India).These ingredients were mixed in agate-mortar for 2 hours.
It was again mixed in a wet atmosphere (methanol) for 3 hours to get homogeneous
mixtures. These mixtures were then calcined at different temperatures in alumina crucibles.
Grinding and calcination was then repeated till the formation of the compounds is
confirmed by X-ray diffraction (XRD technique). The calcined powders were then mixed
with PVA (binder), and were used to make cylindrical pellets of diameters of 10 mm and
thickness of 1-2mm under a uni-axial pressure of 5x106 N/m2 using a hydraulic press. The

36
Chapter 2 Sample preparation and experimental techniques

pellets were then sintered at different temperatures for different compounds. The
calcination and sintering temperatures of the compounds are shown in Table 2.1. During
high-temperature sintering the binder becomes volatile. Using scanning electron
microscope (SEM), the surface- morphology of gold-plated pellets was recorded. Highly
conducting silver paste was coated on both the surface of the disc, which acts as electrode.
The pellets were dried at 150oC for 5 hrs to remove moisture before carrying out electrical
measurements.

Table 2.1: Calcination and sintering temperature of the compounds.

Materials compositions Calcination Sintering

temperatures (oC) temperatures(oC)

x=0.0 780 800

x=0.1 800 800
(Bi1-xLix)(Fe1-xNbx)O3 x=0.2 800 800
x=0.3 800 800
x=0.4 800 800
x=0.5 800 800
x=0.1 800 820
x=0.2 800 820
(Bi1-xNax)(Fe1-xNbx)O3 x=0.3 800 820
x=0.4 800 820
x=0.5 800 820
x=0.1 880 900
x=0.2 880 900
(Bi1-xKx)(Fe1-xNbx)O3 x=0.3 900 900
x=0.4 1000 1000
x=0.5 1000 1000

2.1.3 (B) Preparation of the ceramics-polymer composites

PVDF-ceramic composites were prepared using the following procedures as summarized

below.

37
Chapter 2 Sample preparation and experimental techniques

Solution casting method:

Bulk PVDF granules were purchased from HiMedia Laboratories Pvt.Ltd. Mumbai. The N-
methyl-2-pyrrolidone (NMP) was AR grade from Leonid Chemicals Pvt.Ltd, Bangalore.
The reason for using a polar solvent like NMP is to maintain the polarity of the polymer in
the solution. PVDF granules were weighed by using a digital balance.

Fig. 2.2: Solution casting of PVDF-ceramic composites.

The PVDF-ceramic mixed solution was made using NMP as the solvent. All the materials
were used without further purification. Solution cast technique was used to prepare the
polymer-ceramic composite.

PVDF ADD HEAT ADD

20 ml PVDF CALCINED
GRANULES NMP ~70oC SOLUTION CERAMIC

THIN FILM OF
PEEL EVAPORATE AT STIRRED FOR
POLYMER-
ROOM 5-6 HOURS
CERAMIC
TEMEPRATURE
COMPOSITE IS
FORMED

Fig. 2.3: Flow chart for the preparation of ceramic-polymer composite through solution
casting technique.

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Chapter 2 Sample preparation and experimental techniques

The polymer (PVDF) and ceramic were taken in a ration of 1:1. PVDF granules were first
dissolved in NMP at a temperature of ~ 70-80oC on a hot plate under constant stirring with
the help of a magnetic stirrer for nearly an hour until complete dissolution of the PVDF
granules. Then the calcined powder was added slowly to the solution in order to avoid
powder sedimentation or agglomeration and again stirred for 5-6 hours. The homogeneous
suspension was then poured in a glass petri dish and then allowed to dry in air for few days
to remove solvent traces. The thin film was then peeled off from the petri dish.

2.2 Experimental Techniques

A single experiment is not sufficient to characterize the materials. Different aspects of the
materials like structure, surface morphology, thermal, electrical, mechanical, optical etc.
should be studied in details in order to understand the chemistry and physics of materials.
In order to derive a better understanding of the structure-property relationship of solids,
various experimental techniques are adopted. The basic principles, preliminary descriptions
and uses of important experimental methods along with the scope of the present
investigation are furnished in the following sections.

2.2.1 X-ray Diffraction (XRD)

Physical properties of solids such as electrical, optical, magnetic, ferroelectric, etc. depend
on the atomic arrangements in them. Hence structure of a crystal is an indispensible part of
the characterization of the materials. X-ray diffraction (XRD) technique is a powerful tool
used for proper structural analysis. XRD patterns are used to establish the atomic
arrangement or structure of the materials because the d spacing of diffraction planes is of
the order of wavelength (λ) of x-ray. Reflection occurs for different orders (n) only at the
precise values of angle θ, which satisfies the Bragg equation given by n λ = 2dsin θ.
Bragg’s law relates the wavelength of electromagnetic radiation to the diffraction angle and
the lattice spacing in a crystalline sample.

When monochromatic beams of x-rays fall on a powder sample of polycrystalline material,

the randomness of crystallite orientation always allows a fraction of the sample to be
suitably oriented with respect to the incident beam, which in turn enables an arbitrary
diffraction line to be observed. In such a sample, the various lattice planes also present in

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Chapter 2 Sample preparation and experimental techniques

every possible orientation. Therefore, at least some crystals must be oriented at the Bragg
angle, thus diffraction occurs for these crystals and planes. The most important use of the
powder method is in the qualitative identification of crystalline phase or compounds. The
accurate determination of inter-planar spacing of a plane (h k l) (d) and lattice parameters
(a, b, c, α, β and γ) provide information regarding the various properties of a material. The
calculation of d using peak position can be carried out using a general formula [200, 201]:

1 1
= 𝑉 2 [h2b2c2sin2α + k2c2a2sin2β + l2a2b2sin2γ + 2abc {kla (cosβcosγ – cosα) +
𝑑 ℎ2 𝑘𝑙

hlb (cosαcosγ – cosβ) + khc (cosαcosβ – cosγ)}]

X-rays are produced in a cathode-ray tube by indirectly heating a filament to produce

electrons. When a voltage is applied these electrons are accelerated towards a target thereby
bombarding the target with electrons. When electrons having sufficient energy dislodge
inner shell electrons of the target, characteristic X-ray spectra are produced. These spectra
consist of several components, the most common being Kα and Kβ. Kα consists of Kα1 and
Kα2 where Kα1 has a slightly shorter wavelength and twice the intensity as Kα2. The specific
wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). The wavelength of
Kα1 and Kα2 are very close and hence an average of the two is taken. For single-crystal
diffraction Copper (with CuKα radiation = 1.5418 Å) is considered as one of the most
common target material. To produce monochromatic X-rays required, crystal
monochromater is needed. These X-rays are collimated onto the sample and when the
sample and detector are rotated, the intensity of the reflected X-rays is recorded. When the
geometry of the incident X-rays striking the sample satisfies the Bragg Equation, a peak in
intensity occurs due to constructive interference. The sample is scanned through a range of
2θ angles in all possible diffraction directions of the lattice because the powdered material
is randomly orientated. This X-ray signal is recorded by a detector and converted to a count
rate which is fed to computer monitor. The diffraction peaks are then converted into d-
spacing for identifying the material as each material has a set of unique d-spacing which is
then compared with standard reference patterns.

40
Chapter 2 Sample preparation and experimental techniques

Fig. 2.4: Reflection and Transmission geometry in Powder X-ray diffraction.

Powder diffraction data can be collected using either transmission or reflection geometry, as
shown in Fig. 2.4. In a powder sample, the particles are randomly oriented; hence these two
methods (transmission and reflection) will yield the same data.

In the present study, X-ray diffraction of high resolution (Bruker's X-ray Diffraction D8-
Discover) is used with a step size of 2o / min.

Fig. 2.5: Bruker's X-ray Diffraction D8-

Discover instrument.

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Chapter 2 Sample preparation and experimental techniques

 Applications

 Qualitative and quantitative phase analysis of the materials can be studied.

 The crystalline structural parameters are obtained. By the refinement of least-
squares method the unit cell parameters for crystals of any structure may be
specified.
 Study of phase composition, structure, dispersity, crystallinity of the short-range
order in the amorphous and ultra-dispersed materials can also be done.

2.2.2 Scanning electron microscope (SEM)

The scanning electron microscope uses a highly

focused electron beam which is scanned on the surface
of the sample to produce high-quality images of the
surface topography. It offers a very high magnification
with very high-resolution. It gives information about
external morphology (texture), chemical composition,
and crystalline structure and orientation of materials
forming up the sample. With the help of a small
electron probe (a beam of electrons) it produces
micrographs by scanning the surface. A schematic
diagram of scanning electron microscope is shown in
Fig. 2.6.

Fig. 2.6: Schematic diagram of scanning electron microscope.

Image formation in scanning electron microscope occurs in following manner. When a

beam of highly energetic electrons strikes the sample, the secondary electrons, x-rays and
back-scattered electrons are ejected from the sample. These secondary electrons emitted are
collected and converted into a current that is amplified to produce a signal voltage. This
signal is passed to a cathode-ray tube (CRT) where it determines the potential of the

42
Chapter 2 Sample preparation and experimental techniques

regulating or modulating electrode which controls the current in the cathode ray tube. As a
result, a point on the screen of the CRT is formed whose brightness is controlled by the
current reaching the collector. The basic units of a scanning electron microscope are: (a)
electron-optical columns together with appropriate electronics, (b) the vacuum system,
which includes the specimen chamber and stage and (c) signal detection and display
system. The electron column contains magnetic lenses whose function is to focus the
electron beam. Two sets of scanning coils are coupled with appropriate scan generator and
cause the beam to be deflected over the specimen surface in a raster like pattern. The
specimen chamber is designed in such a way that the various types of movements such as
translation, rotation and tilting of the specimen in desired direction can be done in the
chamber. The normally attained orientations in the specimen stages are translation, 360 o
rotation and provision for tilting the specimen. The detection system used in SEM depends
on the interaction of primary electron beam with the specimen. The different effects like
secondary electron emission, reflected or back scattered electron current, x-ray production
and cathode luminescence etc. are usually observed. All of the signals can be detected,
amplified and used to control the brightness of the cathode ray tube (CRT). The deflection
of the electron beam in the CRT is controlled by the same scan generator, which determines
the position of the electron beam on the sample. Thus SEM is a powerful technique for
point to point scanning of the small region such as grain and grain boundaries. The
interaction of high-energy electrons with specimen leads to the excitation of variety of
signals, which can be used in the characterization of microstructure etc.

In the present study, sintered pellet of each compound has been taken for microscopic
study. The surface of the pellet is gold plated by a vacuum coating technique. The
micrograph at different magnifications was recorded using JEOL JSM- 5800 scanning
electron microscope.

2.2.3 Dielectric study

When a dielectric material is placed in an electric field, due to induced dipole moment
polarization takes place. This induced dipole moment (P), is proportional to the applied
electric field, (E) and is expressed as,

43
Chapter 2 Sample preparation and experimental techniques

P = αE

Where α is a constant of proportionality known as polarizability of the atom or molecule.

In dielectric materials, the different allowed polarizations are electronic polarization, ionic
polarization, dipolar (orientation polarization) and interfacial (space charge) polarization.
The macroscopic behavior of a dielectric can be understood by placing a dielectric in
between a parallel plate capacitor. The capacitance (C) of a capacitor with the dielectric is
expressed as

C = εrε0A/d

Where εr=ε/ε0 is the dielectric constant (relative permittivity) of the dielectric, ε is the
permittivity of the dielectric, ε0 (8.85x10-12 F/m) is the permittivity of free space, A and d
corresponds to the area and thickness of the conducting plates respectively.

When a dielectric material is placed in an alternating field, these polarizations are set up
which gives rise to dielectric constant. A phase shift occurs between the driving field and
the resulting polarization. A loss current component appears which gives rise to the
dielectric loss. Polarization (P) and electric displacement (D) varies periodically with time
and lag behind the electric field E, so that
D = D0cos (ωt - δ) = D1cosωt + D2sinωt

Where δ is the phase angle and slightly less than 90°,

D1 = D0cosδ and D2 = D0sinδ
The ratio of displacement vector to electric field (D0 / E0) is, in general, frequency
dependent for most of the dielectrics. Hence, we can introduce two frequency-dependent
dielectric constants:
ε'r(ω) = (D0 / E0) cosδ
ε''r(ω) = (D0 / E0) sinδ

When an alternating potential V=V0ejωt is applied, the total current in the dielectric is given
by

I = dQ/dt = d(CV)/dt = jωεrC0V

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Chapter 2 Sample preparation and experimental techniques

As εr is complex quantity (i.e., εr = ε'r - j ε''r,) I can be written as

I=jω (ε'r - j ε''r) C0V = ω ε''r C0V + jω ε'r C0V = I1 + IC

The value of real component ε'r determines the out- of-phase component of the current and
the value of imaginary component ε''r determines the in-phase component of the current.

tangent loss can be expressed as,

tan δ = I1/IC = ε''r/ ε'r

The total current I through the capacitor can be resolved into two components, a charging
current (I1) in quadrature with voltage and conduction current IC in phase with the voltage.
The vector resolution of the total current is shown in Fig. 2.7.

j ω εrC0V
j ω ε'rC0V

ω ε''rC0V

Fig. 2.7: The vector resolution of ac current in a capacitor.

For a parallel plate capacitor with sinusoidal applied voltage, loss current density is given
by
Jl = ω ε0 ε ''r V = ζ V
Where ζ = ω ε'r ε0 tan δ is the dielectric conductivity. The effective dielectric conductivity
depends upon frequency and is greater than dc conductivity. The dielectric loss (tangent
loss) is an important criterion for the usefulness of a dielectric as an insulator for
applications. So, for application purposes where high capacitance is needed, the materials
should possess high dielectric constant and low tangent loss (tan δ). The dielectric
properties of ferroelectrics depend on the field strength at which they are measured.

45
Chapter 2 Sample preparation and experimental techniques

In the present investigation the dielectric measurements have been carried out using PSM
1735:N4L impedance analyzer (Fig. 2.8) with indigenously developed two terminal sample
holders. The working frequency range of the LCR meter 100 Hz to 35MHz. The heating of
the small vertical furnace can be controlled by a variac (transformer), and can be heated to
a maximum temperature of 500oC.

Fig. 2.8: PSM 1735:N4L impedance

analyzer.

2.2.4 Study of spontaneous polarization

Ferroelectrics are materials that possess

spontaneous electric polarization in the
absence of an external applied electric and
the direction of the polarization can be
reversed by an electric field. Polarization (P)
is the electric dipole moment per unit
volume, and can be related to dielectric
displacement (D) with the help of a linear
expression, D = P + ε0E where ε0 called as
the permittivity of free space and its value is
8.854x10-12 Coulomb/volt. When the term
ε0E in the above expression is very small as
compared to P (as in the case of most
ferroelectric materials), D is nearly equal to
P. Fig. 2.9 shows the P as a non-linear
functions of E (P-E hysteresis loop). Fig. 2.9: P-E hysteresis loop

46
Chapter 2 Sample preparation and experimental techniques

Fig. 2.10: Schematic diagram of a Sawyer-Tower circuit for polarization measurements.

Based on a paper by Sawyer and Tower the method of polarization measurement is done
[202]. Fig. 2.10 shows a schematic Sawyer-Tower circuit. With the help of a resistive
divider the alternating field applied across the sample is attenuated. The sample is
connected in series with a large capacitor and hence current is integrated into charge. To get
P-E loop both these voltages are then fed into X and Y axes of an oscilloscope. By
recording these traces using photographs screen numerical analysis became very difficult.
This circuit was then modified by Diamant et. al. [203] and they included variable resistive
and capacitative components resulting in only the non linear part.

Fig. 2.11: Radiant Ferroelectric Tester

47
Chapter 2 Sample preparation and experimental techniques

Before tracing the hysteresis loops, the ferroelectric materials are poled by applying an
electric field. Poling is done to align the randomly oriented electric dipoles in a specified
direction. The process of polling of ferroelectrics is to switch reverse domains below
transition temperature (TC) with higher electric fields than coercive field.
In the present study the polarization (hysteresis loop) of the sample at various fields was
obtained using hysteresis loop tracer of M/S Radiant Technologies, US.

2.2.5 Impedance and Modulus Spectroscopy

The electrical behavior of a multiferroic material needs to be properly analyzed to decide its
suitability for multifunctional applications. In order to study the polarizability and structural
phase transition, two types of experimental techniques are needed; one sensitive to long
range cooperative phenomena, the other sensitive to changes in the local order. One such
technique is dielectric and impedance spectroscopy. The method mainly involves analyzing
data in terms of different complex formalisms like complex impedance (Z*), complex
admittance (Y*), complex electric modulus (M*) etc. They are in turn related to one
another as follows:
Complex impedance, Z*(ω) = Z'- j Z'' = RS-1/ jω CS…………………………. (2)

Complex permittivity, є*(ω) = є'- j є''………………………………………… (3)

Complex modulus, M*(ω) = M'+ j M''=1/ є* = j ω є0Z* = j ω є0 (1/Y*)……… (4)

Complex admittance, Y*(ω) = Y' + j Y'' = 1/RP + j ω CP…………………….... (5)

tan δ = є''/ є'…………………………………………………………………….. (6)

Where ω is the angular frequency, RS and CS are the resistance and capacitance in series;
RP and CP are the resistance and capacitance in parallel. The (Z', M', є') and (Z'', M'', є'') are
the real and imaginary parts of impedance, modulus and permittivity respectively. j = √-1 is
the imaginary factor.

The complex impedance spectroscopy is a non-destructive method used for investigation of

the electrical properties of materials [204]. The main advantages of the techniques are: (i) it
includes simple electrical measurements, (ii) the measurements can be taken by using

48
Chapter 2 Sample preparation and experimental techniques

arbitrary electrodes, (iii) the results can be correlated with the properties such as
composition, microstructure, dielectric properties, chemical reaction etc. of the sample and
(iv) the contribution of grain and grain boundary resistance can be well separated of the
polycrystalline samples. AC measurements are often made with a Wheatstone bridge type
of apparatus (Impedance analyzer or LCR meter) in which the resistance R and capacitance
C of the samples are measured and balanced against variable resistors and capacitors. The
frequency dependence of impedance |Z| and the phase difference (θ) between the voltage
and current are measured in this technique. In impedance plot the imaginary part of the
impedance Z''= |Z| cosθ is plotted against the real part Z'= |Z| sinθ on a complex plane.

(a) (b)

Fig. 2.12: (a) The impedance plot for a circuit of a resistor and a capacitor in parallel and
(b) the corresponding equivalent circuit.

(a) (b)

Fig. 2.13: (a) The impedance plot for an ideal polycrystalline sample and (b) the
corresponding equivalent circuit.
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Chapter 2 Sample preparation and experimental techniques

An impedance plot with linear scale is used to analyze the equivalent circuit as follows.
Impedance plot of a pure resistor is a point on real axis and that of pure capacitor is a
straight line coinciding with the imaginary axis.

The impedance of a parallel RC combination is expressed by the following relation,

Z* = Z' - jZ'' = R / (1+ jω RC)
After simplification, one gets
(Z' – R/2)2 + Z''2 = (R/2)2
This represents the equation of a circle with radius R/2 and center at (R/2, 0). Thus, a plot
of Z' vs. Z'' (as parametric function of) will result in a semicircle of radius R/2 as shown in
Fig. 2.12 (a) and the equivalent circuit is shown in Fig. 2.12 (b). (This plot is often called a
Nyquist plot).
The time constant of the simple circuit is defined as t = RC = 1/ωm.
This corresponds to the relaxation time of the sample and the characteristic frequency lies
at the peak of the semi-circle. In a polycrystalline sample, the impedance plot exhibits an
arc at high frequency corresponding to the bulk property of the sample, an arc at low
frequency corresponding to the grain boundary behavior and a spike at the lowest
frequency corresponds to the electrode effect. Fig. 2.13 (a) shows a typical impedance plot
for a polycrystalline sample and Fig. 2.13 (b) represents the equivalent circuit. In the
present work, impedance measurements have been performed using PSM 1735:N4L
impedance analyzer 10 μHz to 35 MHz at different temperatures.

2.2.6 AC and DC Conductivity studies

When an alternating electric field V is applied across a capacitor, an alternating current I

will flow through it having value I= jωεC0V, provided that the dielectric is perfect one
[205]. The ac conductivity of the dielectric can be deduced from the real part of current
density passing through it. The ac conductivity of the dielectric can be deduced from the
real part of current density passing through it. The ac conductivity (ζac) and activation
energy (Ea) of the compounds were calculated from the measured dielectric data using
Arrhenius equation,

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Chapter 2 Sample preparation and experimental techniques

ζ = ωεrε0tanδ = ζ0exp (-Ea/KT)

Where ε0 is the vacuum dielectric constant, ω is the angular frequency and k is the
Boltzmann constant.

The dc (bulk) electrical conductivity was calculated using the relation, ζdc = t/RbA, where
Rb is the bulk resistance found from impedance plot, t is the sample thickness and A is the
surface area of the sample.

An electrometer (Fig. 2.14) is an electrical instrument designed to detect very small

voltages and currents. The quadrant, Lindermann, Hoffman, and Wulf electrometers
measure electrical potential between charged elements.

These instruments show a sensitivity of about

0.01 volt. A vacuum-tube electrometer is a
device which is subjected to drift and is
comparatively more sensitive than the above
discussed electrometers. It is a dc amplifier
which has a capability of measuring upto 10-
15
amperes which means about 10,000 electrons
per second. Now-a-days the electron tube is
being replaced with a pair of junction field-
effect transistors. Fig. 2.14: Electrometer

In the present study I~V characteristics was recorded at different temperatures (from room
temperature up to 500oC) from zero to 100V using Keithley's 5½-digit Model 6517B
Electrometer. It is a high resistance meter which offers high accuracy and sensitivity. It
simplifies measurement of high resistance and resistivity of insulating materials.

Magnetic Study:

By studying hysteresis loop of materials a lot of information about the magnetic properties
of materials can be obtained. A hysteresis loop (referred to as M - H loop shown in (Fig.
2.15) shows the relationship between the induced magnetic field (H) and magnetization
(M). From the hysteresis loop, a number of primary magnetic properties of a material can
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Chapter 2 Sample preparation and experimental techniques

be determined such as (a) retentivity, (b) residual magnetism, (c) coercive field, (d)
permeability, and (e) reluctance. Many types of magnetometers have been developed and
are commercially available such as SQUID (Super conducting quantum interference
device), VSM (vibrating sample magnetometer), Inductive pick up coils, torque
magnetometry, faraday force magnetometry, optical magnetometry, etc.

Fig. 2.15: M-H hysteresis loop

A SQUID is a very sensitive magnetometer which is used

to to measure extremely small magnetic fields. It is based
on superconducting loops containing Josephson junctions.
SQUID are mainly of two types: (i) direct current (DC) (ii)
radio frequency (RF). RF SQUID contains only
one Josephson junction and this makes it cheaper to
produce, but is less sensitive.

Fig. 2.16: working principle of SQUID

In 1962 Brian David Josephson postulated the Josephson Effect. In 1963 at Bell
Laboratory John Rowell and Philip Anderson made the first Josephson junction [206]. In
1964 Jaklevic et.al. [207] of Ford Research Lab invented DC SQUID. It is based on the
DC Josephson Effect and in the superconducting loop it has two Josephson junctions in
parallel. Inner diameter of loop is nearly equal to 100 μm. It is usually made from either an
alloy of lead and gold or indium, or pure niobium. Current flows around the loop through

52
Chapter 2 Sample preparation and experimental techniques

both Josephson junctions and electrons tunnel through them and interfere. The net
potential difference across the loop can be measured.

VSM is combined with SQUID to improve its sensitivity. In the present study magnetic
hysteresis of the compounds was measured using Ever Cool SQUID VSM DC
magnetometer. The Quantum Design MPMS SQUID VSM EverCool system consists of an
integrated pulse-tube cryocooler-dewar system which recondenses the liquid helium
directly within the EverCool Dewar and also liquefies the initial charge of liquid helium
directly from helium gas. Hence any liquid cryogens for the operation are no more required.
It utilizes a 7 Tesla, superconducting, helium-cooled magnet. It operates in the range of 1.8
K to 1000 K and its magnetic field range is -70 kOe to +70 kOe.

Fig. 2.17: Cutway view of EverCool SQUID VSM DC magnetometer.

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