Exploring the Structural and Electrical Properties of Co-Doped Mn0.4Zn0.

6
Oxides

Aiman Tariq FA23-RPH-007

Hira Abbasi FA23-RPH-031

Kinza Abbasi FA23-RPH-037

Course Instructor: Dr. HannanYounis

Subject Supervisor: Dr.M.Anis ur Rehman

Subject Supervisor’s Signature: ______________

Course Instructor’s Signature: ______________ Date:

Applied Thermal Physics Laboratory (ATPL),

Department of Physics, COMSATS University Islamabad, Pakistan
1
Acknowledgement

2
 Abstract

Cobalt doped manganese zinc ferrite nanoparticles spinel structure have attracted much attention
because of their excellent structural, magnetic and electrical properties. Our goal is to study the
structural and electrical properties of Cobalt doped Zn 0.6Mn0.4-xFe2O4 where (x= 0.0, 0.2)
synthesized by sol-gel method. Sintering of the material was done at 700 ◦C for 3 h . The
characterization of the samples was done by X-ray diffraction (XRD) technique used to analyze
the structural properties of the sample which confirmed the cubic structure. AC electrical
analysis such as AC conductivity (σ), dielectric constant (ε), dielectric loss ( and loss tangent tan
(δ) were done under the frequency range of 20 Hz to 3 MHz at room temperatures with the LCR
system. DC electrical analysis were done by using temperature range of 400°C to 30°C with the
decreasing trend. DC electrical analysis were done by using current voltage system (two probe
method). Research has been done on conductivity and activation energy in relation to
temperature in DC electrical properties.

3
Contents

4
5
Introduction

1.1 Nano particles

A nanoparticle is a small particle which has range between 1 to 100 nanometers, which cannot be
seen from naked eye. The material properties change as their size approaches the atomic scale.
This is due to the surface area to volume ratio increasing, resulting in the material’s surface
atoms dominating the material performance. Nano particles have a very large surface area to
volume ratio compared to bulk material like powder, plate sheets. This increases reactivity and
makes them highly effective in applications like catalysis and drug delivery. Quantum
mechanical effects become more significant at nano scale which effect their electronic, optical
and magnetic properties. Nano particles can be made from metals (carbon, silver), metal oxide
(titanium oxide, zinc oxide), carbon based materials and polymers. Nanoparticles have different
shapes like tubes, rods, spheres. [1]

Depending on their shape, size and structure; nanoparticles have different applications like nano
particles are used in cancer therapy and vaccines, magnetic nano robots, nano motors, food
safety, solar cells, hydrogen fuel cells etc. [2]

1.1.1 Classification of nano particles

There are different types of nano materials depending on their shape, size and structure. They
can range from zero dimension to three dimension.

Nano particles can be classified into different categories according to dimension.

1. Zero-dimensional (0D): (for example, nanoparticles)

2. One-dimensional (1D): (for example, nanotubes & nano rods)

3. Two-dimensional (2D): (for example, graphene)

4. Three-dimensional (3D): (for example, nano prisms & nano flowers) [3]

1.1.2 Types of Nano particles

There are many different type of nano particles which are given below:

6
  Metal oxide nano particles
 Ceramic nano particles
 Polymeric Nano particles
 Lipid-based Nano particles
 Carbon-based Nano particles

Our concerned topic is ferrite which belongs to the category of metal oxide Nano particles

1.1.3 Ferrites

A ferrite is a magnetic ceramic material containing iron oxide (Fe 2O4).They are hard, brittle, grey
or black in colour and polycrystalline which means they are made up of many tiny crystals. They
are made up of iron oxide (Fe2O3) and one or more additional metals like zinc, manganese. Ferric
oxide reacts with a variety of different metals like aluminum, manganese, copper, nickel, cobalt
and even iron itself to generate ferrites. They are ferromagnetic, which means they are attracted
by magnetic field and can be magnetized to become permanent magnet. Compare to many
ferromagnetic materials, most ferrites cannot conduct electricity, making them useful in
like magnetic cores for transformers to suppress eddy currents.[4]

1.1.4 Structure of ferrite

Ferrite have spinel structure instead of normal spinel structure. The B cations occupy one-eighth
of the tetrahedral holes, whereas the A cations occupy one-fourth of the octahedral sites. The
remaining one-fourth is taken by the B cation.

Figure 1.1 Structure of Ferrite

7
1.1.5 Classification of ferrite

Ferrites can be divided into two categories based on their magnetic coercivity, their resistance to
being demagnetized [5]

 Hard ferrites
 Soft ferrites

Hard ferrites

Hard ferrites have high coercivity, so they are difficult to demagnetize. Iron oxide and barium
carbonate or strontium carbonate are used in manufacturing of hard ferrite magnets [6]. The high
coercivity means the material is very resistant to become demagnetize, which is an important
characteristics of permanent magnet. They also have high permeability. They are cheap and used
in household products such as refrigerator magnets, loud speakers and all small electric motors
[6].

Figure 1.2 Hard ferrites

Soft Ferrites

Soft ferrites have low coercivity, so they easily change their magnetization and act as conductors of
magnetic fields. Soft ferrites are not suitable to make permanent magnet because of low coercivity.
They have high permeability so they can conduct magnetic fields and are attracted to magnets but
when the external magnetic field is removed, the remanent magnetization does not tend to persist.
This is due to their low coercivity. The low coercivity also means the material's magnetization can
easily reverse direction without dissipating much energy (hysteresis losses), while the material's
high resistivity prevents eddy currents in the core, another source of energy loss. Because of their
comparatively low core losses at high frequencies, they are extensively used in the cores

8
of RF transformers and inductors in applications such as switched-mode power
supplies and loopstick antennas used in AM radios. [7]

Figure 1.3 Soft ferrites

Types of ferrites on the basis of crystal structure

 Garnet ferrites
 Hexagonal ferrites
 Ortho ferrites
 Spinel ferrites

Our concerned topic is to study and characterize spinel ferrites so we will explain spinel ferrites
in detail.

Spinel ferrites

In recent years, spinel ferrites MFe 2O4 (M=Co, Ni, Mn, Mg, Cu and Zn) have attracted the attention of
many researchers because of their unique characteristics and applications in various fields. The specific
properties of spinel ferrite, such as structural, optical, high electrical resistance, high chemical/thermal
stability, magnetic, high permeability, and mechanical properties makes them unique. The crystal
structure of spinel ferrite consists of interstitial spaces with octahedral (A) and tetrahedral (B) sites
where oxygen and other metal ions are positioned in tetrahedral position in which metal ions fill in
unequal crystallographic positions which determines the magnetic properties [8]. Due to their feature,

9
spinel ferrites play some roles such as in biomedical fields, catalysts, chemical sensors, data storage
devices, magnetic actuators, magnetic ceramics, magnetic hyperthermia, manufacture contaminant
nano-adsorbents, magnetic resonance imaging (MRI), photo catalyst in wastewater treatment, power
transformers, sensing applications, solar cells, transducers, storage devices, and super capacitors [9]

Figure 1.4 Cubic Spinel Ferrite

Spinel ferrites are divided into three further types depending on their crystal structure

 Normal ferrites
 Inverse spinel ferrites
 Complex spinel ferrites

Normal ferrites

In normal spinel ferrites, the metal cations occupy two different sites: A-site occupied by divalent metal
ions and B-site occupied by trivalent metal ions.

Example: Magnetite (Fe₃O₄), Zinc ferrite (ZnFe₂O₄), Nickel ferrite (NiFe₂O₄), Manganese ferrite
(MnFe₂O₄).

Inverse spinel ferrite.

In the inverse spinel ferrite, distribution of metal cation is different from normal ferrite. One half of the B-
site are moved to the tehtrahedral A-site making it occupied by both divalent and trivalent ions. The
remaining half of the B-site remains at original octahedral site.

10
Example: Cobalt ferrite (CoFe₂O₄), Copper ferrite (CuFe₂O₄), Lithium ferrite (LiFe₅O₈)

Complex Spinel ferrites

Some spinel ferrites exhibit partially inverted spinel structures where there is partial occupancy or mixing
of cations between the A-site and B-site

Example Mixed metal ferrites like Ni-Zn ferrite (Ni₁₋ₓZnₓ Fe₂O₄), where the ratio of Ni²⁺ to Zn²⁺ in the
A-site can vary.

Manganese Zinc Ferrite:

1.2 Literature Review

S.F. Mansour et.al used Cobalt Zinc Manganese ferrite (Co 0.5Zn0.25Mn0.25CexFe2-xO4) and doped
with Co3+ to control the magnetic and electrical properties. Zinc–manganese (Zn–Mn) ferrites
are considered the most prevalent soft ferrites. Co 0.5Zn0.25Mn0.25CexFe2-xO4 was prepared using
citrate combustion process which were analyze by using XRD, FTIR AND STEM technique.
XRD pattern shows that all dopants easily replaced the Ce 3+/Fe3+ ions without altering the host
ferrite's cubic symmetry. The dielectric loss of the CZMC nano ferrites decreases with Ce 3+
content, indicating that it may be a suitable component for high-frequency applications. The
magnetic and dielectric results reveal that Ce 3+ is an appropriate selection as a substitute for the
Cobalt Zinc Manganese nano ferrites for planar inductor and transformer cores at high-frequency
applications. [11]

S.M. Ansari et al. studied the effect of Manganese-Doping on the chemical and optical
properties of cobalt ferrite nanoparticles (Co 1-xMnxFe2O4). Manganese doped cobalt ferrites were
synthesized using hydrothermal method and characterize by using XRD. The XRD results
clearly show that the Mn-substitution in CFO produces the lattice parameter enhancement,
crystallite size increase, and micro-strain (ε). This indicate that Mn-substitution enables control
over the structure, phase, size and strain of CFMO NPs. The results also demonstrate that the Mn
substitution had a significant impact on the chemical valence state and optical properties. [12]

A.B. Naik, et al. studied Structural, magnetic and electrical properties along with antifungal
activity & adsorption ability of cobalt doped manganese ferrite nano particles (Mn 1-xC0xFe2O4)
which were synthesized using combustion method. The cubic spinel structure of cobalt doped

11
 Manganese ferrite were confirmed by using X-ray diffraction and Fourier transform infrared
spectroscopy. The lattice parameter and unit cell volume for Mn 1-xCoxFe204 were seen to decrease
with increasing cobalt concentration. This decrease in cell parameters may be attributed smaller
ionic radii of Co+2 (0.79 Å and 68.5 Å) replacing a larger ion Mn +2 (0.81 Å and 0.72 Å) at the
tetrahedral site and the octahedral site respectively. Further results showed that cobalt doped
manganese ferrites are cost-effective, a potential candidate for antifungal applications. The
adsorption capacity of the samples was seen to decrease with increasing Co+2 concentration. [13]

Hamnesh Mahajan et. al synthesize and investigate the structural, morphological, and magnetic
properties of the manganese doped cobalt-zinc spinel ferrite (Mn xCo0.5-xZn0.5Fe2O4). The sample
was synthesize using sol-gel auto combustion technique. The single-phase spinel structure with
cubic symmetry was assured by the XRD studies. The synthesized ferrite has a large surface
area, appropriate pore size, pore size dissemination, and the presence of the functional group
which complements its utilization in the super capacitor electrode material. [14]

1.3 Applications

 Ferrites have importance in engineering and technology because they possess spontaneous
magnetic moment below the Curie temperature just as iron, cobalt, nickel.

 Due to very low eddy current losses, ferrites are used as a core of coils in microwave frequency
devices and computer memory core elements.

 Ferrites are used as ferromagnetic insulators in electrical circuits.

 Ferrites like ZnO find low frequency applications in timers. They are also used as switches in
refrigerators, air conditioners, etc.

 Ferrites are used as magnetic head transducer in recording. [15]

1.4 Aims and motivations

Spinel ferrite nanoparticles are among the most widely used nanoparticles. Spinel ferrites are magnetic
materials composed of metal oxides with interesting magnetic properties and excellent biocompatibility,
making them suitable for a wide range of applications. [16]

12
Chapter 2

Synthesis Methods

2.1 Synthesis of nanoparticles:

Nanoparticles are synthesized through various methods depending on the desired properties and
applications. Nanoparticle synthesis methods can be broadly categorized into two main
approaches.

 Top-down approach
 Bottom-up approach

Figure 2.1 Schematic Representation of bottom-up and top-down approaches

2.1.1 Top down approach:

The top-down approach involves breaking down massive bulk materials into nanoscale particles.
It is a subtractive process that involves using chemicals or mechanical forces to break up the
superstructure bulk materials and confine it to a smaller structure. The fundamental drawback of
top-down techniques is that, despite their simplicity, they produce incredibly small, irregularly
shaped particles. This is because it can be challenging to maintain the right size and form of the
particles. [17]
Some of the top-down approaches for the synthesis of nano materials are:
 Mechanical grinding or milling
13
  High energy ball milling
 Sputtering
 Laser ablation
 Thermal evaporation

2.1.2 Bottom up approach:

The term "bottom up approach" describes the process of building a substance molecule by
molecule and atom by atom from the bottom up. The creation of atom-by-atom deposition results
in the self-assembly of molecules and clusters. On the substrate's surface, these clusters come
together to create a self-assembled monolayer. The initial state of matter in any bottom-up
approach is either gaseous or liquid.[18]
Some of the bottom-up approaches for the synthesis of nano materials are:
 Chemical vapour deposition
 Hydrothermal
 Co-Precipitation Method
 Sol gel method

2.1.2.1 Chemical vapor deposition:

Chemical Vapor Deposition (CVD) is a semiconductor method that uses a chemical reaction in a
gas phase to deposit a thin layer of material onto a substrate. In CVD, a gas mixture comprising
the precursor chemicals is poured into a reaction chamber, which holds the substrate. A solid
film is created on the substrate's surface by the reaction of the precursor chemicals.
The semiconductor industry makes extensive use of CVD to deposit thin films of a variety of
materials, including metal films like copper, tungsten, and aluminum, as well as silicon dioxide
(SiO2) and silicon nitride (Si3N4).[19]

2.1.2.2 Hydrothermal method:

The process of hydrothermal synthesis involves the reaction of a solid material with an aqueous
solution in a reaction vessel at high pressure and temperature, which results in the deposition of

14
tiny particles. Any technique based on solution reactions is called hydrothermal. Since water is
utilized as a solvent in this procedure, it is known as hydrothermal. The hydrothermal method
has a great contribution to modern science and technology due to homogenous precipitation, low
cost, friendly environment, easy scaling up, and pure final product. [20]

2.1.2.3 Co precipitation:

The production of nanoparticles in a range of sizes can be achieved with ease using co-
precipitation. Several other strategies have been applied to produce nanoparticles of uniform
size. Magnetite nanoparticles are created by combining a sodium hydroxide nanoemulsion with
an iron source (NaOH). After acetone lysis has been used to remove the nanoparticles, the
surfactant is washed with ethanol. Colloidal nanoparticles show significant super-paramagnetic
and magnetism properties.

2.1.2.4 Sol gel Method:

The sol-gel process is a more chemical method (wet chemical method) for the synthesis of
various nanostructures, especially metal oxide nanoparticles. In this method, the molecular
precursor (usually metal alkoxide) is dissolved in water or alcohol and converted to gel by
heating and stirring by hydrolysis/alcoholysis. Since the gel obtained from the
hydrolysis/alcoholysis process is wet or damp, it should be dried using appropriate methods
depending on the desired properties and application of the gel. [21]

We used sol-gel method to synthesize our material.

2.2 Synthesis Procedure of Zn0.6Mno.4-xCoxFe2O4:

Sol-gel is the method used in our experiment for the synthesis of pure and cobalt doped spinel
ferrites nanoparticles.For the synthesis of the nanoparticles the precursors Manganese nitrate
Mn(NO3)2.H2O, iron nitrates Fe(NO3)3.9H2O, Zinc nitrate Zn(NO3)2.6H2O and Cobalt nitrate
Co(NO3)2.6H2O were used as shown in figure. Ethylene glycol was used as a stabilizing agent in
which these precursors were added in the stoichiometric amount with ratio 1:14. The solution
was stirred for 30 minutes at room temperature. Then raised temperature to 80℃ for 3 hrs.By
keeping on hot plate magnetic stirrer. The solution was slowly turned into viscous gel. This gel

15
was dried at 180℃, which self-ignite to form as burning and prepared powder.This powder was
then grind and calcination at 650℃ for 3 hours and then pressed into pellets. The samples in the
form of pellet were sintered at 700℃ for 3 hrs and then used for further characterizations.

Figure 2.3 Sol gel method for Zn0.6Mno.4-xCoxFe2O4

16
 Chapter 3

Characterization method

3.1 X-Ray Diffraction (XRD):

X-Ray diffraction technique is the most common and efficient method for the determination of
structure and crystallinity of material identification. XRD is an appropriate method to examine
whether a resultant material has amorphous or crystalline nature. Crystalline phases can be
identified by just comparing the inter Planer distance ‘d’ values obtained from XRD data with
the fundamental data in joint Committee on Powder diffraction standards (JCPDS). [22]
The working principle of XRD is based on destructive interference by
satisfying Bragg’s law of diffraction.[23] Bragg’s law is given as fellows,

nλ =2d Sin Ɵ ……… (1)

Whereas,
n= order of diffraction
λ=wavelength of the incident wave
d=interplanar spacing
Ɵ= incident angle between the two parallel rays

Figure 3.1 Bragg’s law

The crystallite size is measured by Debye Scherer formula Equation 1.

D= k𝜆/𝛽𝐶𝑜𝑠𝜃……………. (2)
Whereas,
λ=Wavelength of X-rays (0.154 nm)
𝜃=Bragg’s angle in degrees

17
K=shape factor
β=Full Width Half Maximum (FWHM)

The lattice constant of the cubic structure is calculated by using Eq.(3)

a = d(h2+k2+l2)1/2……………. (3)
(h, k, l) = miller indices
a =lattice constant
3.2 Electrical Analysis
The Wayne Kerr LCR 6440B has been used to measure the electrical characteristics of AC and
DC. Two copper plates served as the electrodes in this technique. First, electrical contact was
made by inserting the sintered pellet between the two copper surfaces. They are then attached to
the meter's probes. At room temperature, measurements of capacitance, impedance phase angle,
and dissipation factor were made for AC electrical analysis. DC conductivity was measured at
regular interval of 10⁰C. The conductivity profile of synthesized samples was observed
on their pellets. LCR meter was used for dielectric and

3.2.1 AC Electrical analysis:

AC electrical properties of sintered pellets were studied as a function of frequency in the range of
20 Hz to 3 MHz at room temperature. Capacitance (C), dielectric loss (), tangent loss (tan ẟ),
Dielectric constant (ε′) were measured using an LCR meter (two probe method). Research has
been done on conductivity and activation energy in relation to temperature in DC electrical
properties [24].

 Two probe method

It is among the most trustworthy techniques for figuring out the resistivity of a substance. The
same terminals must be used for both voltage and current measurements when employing the
two-terminal method. Only 100 to 10 kHz is its frequency range.

 AC Conductivity

AC conductivity of samples (x = 0.0, 0.2) as a function of frequency at room temperature is

shown in below Fig. 4. AC electrical conductivity is calculated by using Eq (4).

18
 ,
σ =ε ⁰ ε tanδ 2 π ……..(4)

when the concentration of Co+2 or Co+3 the coulomb field at its locality increases and the number
of Fe+3 ions in octahedral side decreases, resulting in a lower conductivity value.
 Dielectric Constant
Dielectric constant (έ) of lithium doped magnesium ferrite as a function of frequency from 20
Hz to 3MHz is shown in Fig. 5. Dielectric constant was then calculated by using Eq. (5)

' Cd
ε= …………. (5)
ε0A

Where “C" is capacitance of the pellet, “L" is the thickness of the pellet, "Ɛ0 ′′ is the constant of
the permittivity of free space and “A" is the area of the pellet.

Dielectric constant of all the samples showed universal behavior i.e., it decreased with increase
in frequency. When external electric field is applied with low frequency, polarization occurs.
Dipoles oscillations begin to die out as the frequency is increased and as a result, dielectric
constant decreases.

 Dielectric Loss

Dielectric loss as a function of frequency is shown in Fig. (4.2). Dielectric loss was then
calculated by using Eq. (6)

ε =¿ ε tan δ …….. (6)

″ '

At low frequency range the losses are greater because the electrons have not enough energy for
the exchange of ions, when external field is applied the ions gain more energy and hence loss
losses occur. At high frequency range, the losses become small because the ions have already
enough energy for charge transformation.

 Tangent Loss

Graphs of dielectric loss tangent (tan δ) of Li doped magnesium ferrite is shown in Fig. (4.3).
Dielectric loss tangent was then calculated by using Eq. (7)

19
 ″
ε
tan δ= ' ……… (7)
ε

The samples showed regular trend and its dielectric loss decreased with increase in frequency.
Dielectric loss tangent represents the energy dissipated in polarization process. Polarization
occurs due to the external applied field. Dipoles oscillate with frequency of applied field, which
accounts for energy losses. The losses are maximum when polarization is maximum and dipoles
continue to follow the field. After a certain frequency, dipoles become unable to follow the field
and after this polarization begins to vanish and losses decrease. Relaxation peak, hence, occurs at
jump frequency and shifts towards higher frequency with increase in temperature.

3.2.2 D.C. ELECTRICAL CONDUCTIVITY

The electrical response of the sample to D.C. voltage has been investigated to identify and better
understand the conduction mechanism in this material. In this experiment we measured the
resistivity of sample as a function of temperature, from about 50 ºC up to about 500 ºC, using a
cryostat with a heating stage. The system measures D.C. resistance at different temperatures. The
sample is generally disk shaped bulk material of regular area. Silver/gold coating is performed
on both sides of the disks to make contacts. DC voltage of different level is applied and output
current is read simultaneously at different temperatures. Fig. 8 reveals that D.C. conductivity
increases with increase in temperature and obeys the well-known Arrhenius equation for
semiconducting materials, i.e.

σ dc=σ 0 exp (-E dc/k T) ……… (8)

where σ 0 is the pre-exponential factor, which depends on composition, mobility of diffusing

ions, etc. and Edc is the D.C. activation energy. The activation energy for the conduction
mechanism / process was calculated from the slope of the straightline portion (Fig. 9). The value
of activation energy is found to be Edc = 0.305eV and the value of conductivity varies from 10-9
S/cm to 10-6 S/cm with increase in temperature. [25-27]

20
21
 Chapter 4
4. Result and discussion
4.1 Structural Analysis:
Zinc manganese spinel ferrites material:
The XRD pattern of the calcination sample of Zn0.6Mn0.4Co0.0Fe2O4 and Zn0.6Mn0.2Co0.2Fe2O4 are
shown in fig 4.1and 4,2 The XRD analysis confirms manganese spinel ferrite is cubic Structure.
All most all peaks of XRD patterns have been matched with Ref card no. 01- 089-7557.
Average crystallite size found by using Debye Scherer formula:
Average lattice Constant of Zn0.6Mn0.4Co0.0Fe2O4 = 8.4485±0.05Å
Average crystallite Size of Zn0.6Mn0.4Co0.0Fe2O4 =35.2nm
Average lattice Constant of Zn0.6Mn0.2Co0.2Fe2O4=8.443098±0.00002Å

Table 4.1 The calculated structural parameters of Zn0.6Mn0.4Co0.0Fe2O4

Sr.no. d spacing d spacing (ref) hkl

1 2.53982 2.54569 311

2 1.548579 1.49254 440
3 2.69550 310
4 2.98282 2.98509 220
5 3.67924 210
6 1.69516 430
7 1.62222 1.62488 211

Table 4.2 The calculated structural parameters of Zn0.6Mn0.4Co0.2Fe2O4

22
1 2.54228 2.54569 311

2 1.48994 1.49254 440

3 2.97723 2.98509 220

4 1.62266 1.62488 511

5 2.10765 2.11077 400

6 4.88028 4.87463 111

7 1.71902 1.72344 422

X-ray diffraction study confirms that cubic spinel structure exists as the main phase in all
synthesized composition. All XRD peaks were exactly match with characteristics peak of cubic
spinel structure (Ref card no.01-089-7557.) having most intense peak (311). Zinc (ionic
radii=1.38 Å), Manganese (ionic radii = 0.82 Å), Cobalt (ionic radii=0.56Å) and Iron (ionic radii
= 0.645 Å). Due to smaller ionic radii of Cobalt then manganese the lattice parameter is decrease
favored to reside on octahedral site of spinel structure.

AC Electrical Analysis
AC electrical properties of sintered pellets were studied as a function of frequency in the range of
20 Hz to 3 MHz at room temperature. Capacitance (C), dielectric tangent loss (tan ẟ), Dielectric
constant (ε′) were measured using an LCR meter (two probe method).

Dielectric constant

Dielectric constant (έ) of lithium doped magnesium ferrite as a function of frequency from 20 Hz
to 3MHz is shown in Fig. 5. Dielectric constant was then calculated by using Eq. (3)

' Cd
ε= …………. (3)
ε0A

23
Where “C" is capacitance of the pellet, “L" is the thickness of the pellet, "Ɛ 0 ′′ is the constant of
the permittivity of free space and “A" is the area of the pellet.

Dielectric constant of all the samples showed universal behavior i.e., it decreased with increase
in frequency. When external electric field is applied with low frequency, polarization occurs.
Dipoles oscillations begin to die out as the frequency is increased and as a result, dielectric
constant decreases. The decrease is dielectric constant is explained by four types of polarizations
i.e., atomic, ionic, electronic and interfacial polarizations. All these four types of polarizations
are active at low frequency range and thus there is a high value of dielectric constant, and with
the passage of time these polarizations die out and its value starts decreasing. Thus, the exchange
of electrons (hopping) between Fe2+ and Fe3+ which may not cross grain boundaries due to high
resistance.

Figure 4.1 Dielectric Constant

Dielectric loss

Dielectric loss as a function of frequency is shown in Fig. (4.2). At low frequency range the
losses are greater because the electrons have not enough energy for the exchange of ions, when
external field is applied the ions gain more energy and hence loss losses occur. At high
frequency range, the losses become small because the ions have already enough energy for
charge transformation.

24
 ε =¿ ε tan δ …….. (4)
″ '

Figure 4.2 Dielectric Loss

Tangent Loss

Graphs of dielectric loss tangent (tan δ) of Li doped magnesium ferrite is shown in Fig. (4.3). the
samples showed regular trend and its dielectric loss decreased with increase in frequency.
Dielectric loss tangent represents the energy dissipated in polarization process. Polarization
occurs due to the external applied field. Dipoles oscillate with frequency of applied field, which
accounts for energy losses. The losses are maximum when polarization is maximum and dipoles
continue to follow the field. After a certain frequency, dipoles become unable to follow the field
and after this polarization begins to vanish and losses decrease. Relaxation peak, hence, occurs at
jump frequency and shifts towards higher frequency with increase in temperature.

″
ε
tan δ= ' ……… (5)
ε

25
 Figure 4.3 Tangent Loss

AC Conductivity

AC conductivity of all samples (x = 0.0, 0.2) as a function of frequency at room temperature is

shown in below Fig. 4. AC electrical conductivity is calculated by using Eq (6).

″
σ =2 πf ε 0 ε ……..(6)

Figure 4.4 AC Conductivity

26
27
28
 Chapter 5
Conclusion
Cobalt doped manganese Zinc ferrite Zn0.6Mn0.4-xFe2O4 (x = 0.0, 0.2) were successfully
synthesized by using sol-gel method. XRD shows that crystal structure of Cobalt doped
manganese Zinc ferrite (Zn0.6Mn0.4-xFe2O4) is cubic.

29
References

[1] M. Zhu, Z. Luo, A. Pan, H. Yang, T. Zhu, S. Liang, G. Cao, N-doped one-dimensional carbonaceous
backbones supported MoSe2 nanosheets as superior electrodes for energy storage and conversion, Chem.
Eng. J. 334 (2018) 2190–2200

[2] Debele, Tilahun Ayane; Yeh, Cheng-Fa; Su, Wen-Pin (15 December 2020)

[3] Singh Chouhan et al., 2021

[4] Spaldin, Nicola A. (2010). Magnetic Materials: Fundamentals and Applications, 2nd Ed.
Cambridge University Press. p. 120. ISBN 9781139491556.

[5] Connor, Nick (2023-07-24). "Ferrite | Formula, Properties & Application". Material
Properties. Retrieved 2024-03-29.

[6] "Ferrite permanent magnets". arnoldmagnetics.com (product catalog). Arnold Magnetic

Technologies. Archived from the original on 14 May 2012. Retrieved 18 January 2014.

[6] "Amorphous magnetic cores". hilltech.com (product catalog). Hill Technical Sales. 2006.
Retrieved 18 January 2014.

[7] Facile synthesis and temperature dependent dielectric properties of MnFe204

nanoparticles. AIP Conference Proceedings. Vol. 2115. 2019.
p. 030104. doi:10.1063/1.5112943

[8] ] A.H. Cahyana, A.R. Liandi, Y. Yulizar, Y. Romdoni, T.P. Wendari, Green synthesis of
CuFe2O4 nanoparticles mediated by Morus alba L. leaf extract: crystal structure, grain
morphology, particle size, magnetic and catalytic properties in Mannich reaction, Ceram. Int. 47
(2021) 21373–21380, https://doi.org/ 10.1016/j.ceramint.2021.04.146.

[9] R. Kumar, R. Kumar, P. Kumar, M. Singh, A. Soam, Materials Today : proceedings

Synthesis of nickel ferrite for supercapacitor application, Mater. Today Proc. (2022) 2–5,

30
[11] ] N.S. Al-Bassami, S.F. Mansour, E. Abdel-Fattah, M.A. Abdo, Ce-Co-Mn-Zn ferrite nano
catalyst: a synergetic effect of rare earth Ce3+ on enhanced optical properties and photocatalysis,
Ceram. Int. 49 (12) (2023) 20601–20612. .

[12] S.M. Ansari, B.B. Sinha, D. Phase, D. Sen, P.U. Sastry, Y.D. Kolekar, C.V. Ramana, A.C.S.
Appl, Nano Mater. 2019 (1828) 2.

[13] ] A.I. El-Batal, A.A. Farrag, M.A. Elsayed, &A.M. El-Khawaja, Biodiesel production by
Aspergillus Niger lipase immobilized on barium ferrite magnetic nanoparticles, Bioengineering 3
(2) (2016) 14.

[14] G. Raju, N. Murali, M.S.N.A. Prasad, B. Suresh, D.A. Babu, M.G. Kiran, A. Ramakrishna,
M.T. Wegayehu, B.K. Babu, Effect of chromium substitution on the structural and magnetic
properties of cobalt ferrite, Mater. Sci. Energy Tech. 2 (2019) 78–82

[15] “electrical engineering materials”

[16] ] R. Bilas, K. Sriram, P.U. Maheswari, K.M.M. Sheriffa Begum, Highly biocompatible
chitosan with super paramagnetic calcium ferrite (CaFe2O4) nanoparticle for the release of
ampicillin, Int. J. Biol. Macromol. 97 (2017) 513–525

[17] Z. Vaseghi, A. NematollahzadehNanomaterialsGreen synthesis of nanomaterials for

bioenergy applications, Wiley (2020), pp. 23-82
[18]Abid, Namra, et al. "Synthesis of nanomaterials using various top-down and bottom-up
approaches, influencing factors, advantages, and disadvantages: A review." Advances in Colloid
and Interface Science 300 (2022): 102597.
[19]Jones, Anthony C., and Michael L. Hitchman, eds. Chemical vapour deposition: precursors,
processes and applications. Royal society of chemistry, 2009.

[20]Gan, Yong X., Ahalapitiya H. Jayatissa, Zhen Yu, Xi Chen, and Mingheng Li.
"Hydrothermal synthesis of nanomaterials." Journal of Nanomaterials 2020 (2020): 1-3.

[21]F. Adam, C. Thiam-Seng, J. Andas, J. Sol-Gel. Sci. Technol. 59, 580–583 (2011)

[22]. Krok, F., Abrahams, I., Bangobango, D., Bogusz, W., &Nelstrop, J. A. G.
(1998). Structural and electrical characterisation of BINIVOX. Solid State
Ionics, 111(1-2), 37-43. [27]McMurdie, Howard F., Marlene C. Morris, Eloise H. Evans, Boris
Paretzkin, Winnie Wong-Ng, Lisa Ettlinger, and Camden R. Hubbard. "Standard X-ray

31
diffraction powder patterns from the JCPDS research associateship." Powder Diffraction

[23]Harrington, George F., and José Santiso. "Back-to-Basics tutorial: X-ray diffraction of thin
films." Journal of Electroceramics 47, no. 4 (2021): 141-163.

[24] A.K. Nikumbh, A.V. Nagawade, G.S. Gugale, M.G. Chaskar, P.P. Bakare, The formation,
structural, electrical, magnetic and Mössbauer properties of ferrispinels, Cd1−x NixFe2O4, J.
Material Science 37 (2002) 637-647.

[25] Ferrite material science and technology, Viswanathan B, Murthy VRK, New Delhi: Narosa
Publishing House, p6, 1990.

[26] Fundamentals of the physics of solids- structure and dynamics, volume1, Jeno Solyom, pp
59, 2007, Springer 1, no. 2 (1986): 64-77.

[28]. Krok, F., Abrahams, I., Bangobango, D., Bogusz, W., &Nelstrop, J. A. G.
(1998). Structural and electrical characterisation of BINIVOX. Solid State
Ionics, 111(1-2), 37-43. [27]McMurdie, Howard F., Marlene C. Morris, Eloise H. Evans, Boris
Paretzkin, Winnie Wong-Ng, Lisa Ettlinger, and Camden R. Hubbard. "Standard X-ray
diffraction powder patterns from the JCPDS research associateship." Powder Diffraction

32