PROJECT REPORT

on
" Study of effect of Rare Earth(Ce) substitution on structural properties
Mn- Zn Ferrite Nanoparticles by XRD Technique"
Submitted To

Gondwana University Gadchiroli

In the Partial fulfilment of the award of degree of
MASTER OF SCIENCE IN PHYSICS

By
Ms. Rashmi Anil Arke
[Link].-II Sem-III (Physics)

Under the Supervision of

Mr. Bhaurao R Mr. Sanket A.

Balbudhe Anande Co-
Supervisor supervisor Assistant
Assistant Professor Professor Department of
Department of Physics Physics
Shri Dnyanesh Mahavidyalaya Nawargaon Shri Dnyanesh Mahavidyalaya Nawargaon

DEPARTMENT OF PHYSICS
Shri Dnyanesh Mahavidyalaya Nawargaon
RE-ACCREDITED WITH 'A' GRADE BY NAAC CGPA 3.07
Session: 2024-25
 DECLARATION

I hereby declare that, the work presented in this project titled " Study
of effect of Rare Earth (Ce) substitution on structural properties Mn-Zn
Ferrite Nanoparticles by XRD technique" has been carried out by me under
the supervision of Mr. Bhaurao R. Balbudhe, during the session 2024-25. This
work or its any part is based on original research and has not been submitted by
me to any other University / Institution for the award of any diploma or degree.

Date:
Place: Nawargaon

Ms. Rashmi Anil Arke

[Link].-II (Physics)
 Certificate
This is to certify that, the project report entitled " Study of
effect of Rare Earth (Ce) substitutional on structural properties Mn-Zn
Ferrite Nanoparticles by XRD technique" being submitted by Ms. Rashmi
Anil Arke in partial fulfilment of the requirement for the award of degree of
Master of Science in Physics from Shri Dnyanesh Mahavidyalaya Nawargaon
affiliated to Gondwana University, Gadchiroli is an authentic work carried out
by him/her under my supervision and guidance.

To the best of my knowledge, the matter embodied in the project report has not
been submitted to any other University / Institute for the award of any Degree or
Diploma.

Date:
Place: Nawargaon

Mr. Bhaurao R Balbudhe Mr. Sanket A. Anande

Supervisor Co-supervisor
Assistant Professor Assistant Professor
Department of Physics Department of Physics
Shri Dnyanesh Mahavidyalaya Nawargaon Shri Dnyanesh Mahavidyalaya Nawargaon

Certified by,

Dr. Hemant B. Meshram

Head & Assistant Professor
Department of Physics
Shri Dnyanesh Mahavidyalaya Nawargaon
 Certificate

This is to certify that Ms. Rashmi Anil Arke, is a

bonafide student of [Link].-II Physics of this college for the session of
2024-2025. He/she has completed this project report under the guidance
of Mr. Bhaurao R. Balbudhe on the project entitled of "Study of effect
of Rare Earth (Ce) I substitutional properties Mn-Zn Ferrite
Nanoparticles by XRD technique ", approved by the department.

This project report is being submitted to Gondwana

University, Gadchiroli in the partial fulfilment of the award of Master of
Science in Physics.

Place:
Date:

Dr. Amrut S. Lanje

Principal
Shri Dnyanesh Mahavidyalaya
Nawargaon
 Acknowledgement

Finally, the day has come when flight of my ambitions is ready to take off to turn over my
life with the blessings of Mahadevji. First of all, I bow my head before almighty for his endless
blessings and giving me this life with such a great parents who have worked much beyond their
capacity, because of which now I am capable enough to work and complete this work. I am
indicting my mother Mrs. Gayatri Anil Arke and father Mr. Anil Malkuji Arke for their
endless blessings, encouragement and strength to achieve this academic milestone

I pay my deepest sense of gratitude to respected supervisor Mr. Bhaurao R. Balbudhe, Dept. of
Physics DMVN, for giving me the opportunity to do this research and valuable guidance,
encouragement, support and great supervision. It was a great privilege and honor to work under
his guidance. I entend my sincere gratitude to him for their guidance during entire project work.

I feel acknowledge to deep sense of gratitude to respected and very helpful co-supervisior Mr. S.
A. Anande, Assistant professor, PG Department of Physics, DMVN. For his constant supervision
and provide valuable guidance. He has been helping and encourage me throughout the year. His
vision, sincerity and motivation have deeply inspired me. I am extremely grateful for his support
in completion of project.

I would like to express my gratitude towards Mr. H .B. Meshram, Head, Department of Physics,
Shri Dnyanesh Mahavidyalaya Nawargaon. For giving me a opportunity to work in laboratory
and for providing a necessary research facilities.

I am extremely thankful to my team members Ms. Payal Alewar, Ms. Divyani Dehankar, Ms.
Dezi Nikhare, Mr. Vrushabh Lothe from Shri Dnyanesh Mahavidyalaya Nawargaon for their
help and kind support.

Finally, I am thankful to all those who helped me directly or indirectly during my project
work.

Date:
Place: Ms. Rashmi Anil Arke
 CONTENT
Chapters Page no.

Chapter 1- Introduction
1.1 Magnetism
1.2 Nanoscience and Nanotechnology
1.3 Magnetic Nanomaterials
1.4 Ferrites
1.5 Classification
1.6 Applications of ferrite
1.7 Advantages and Disadvantages of ferrites
1.8 Aim and Objectives

Chapter 2-literature Review

2.1 literature review of Mn-Zn-Ce

Chapter 3- Synthesis Method

3.1 Experiment Method
3.2 Procedure

Chapter 4- Characterization
4.1 characterization of techniques
4.1.1 X-ray Diffraction (XRD)

Chapter 5- conclusion
5.1 Conclusion
5.2 References
 Chapter-1
INTRODUCTION

1
1.1 Magnetism
A physical phenomenon caused by magnetic fields. A force that might also attract or repel
items that have magnetic properties, such as iron, is known as magnetism.
Types of magnetism:
There are five types of magnetism are follows:

1.1.1 Diamagnetism - A magnetism characterized by materials that correspond at right

angles toward a non-uniform distribution magnetic field and partially expel the magnetic field
in which they have been positioned from their interiors. A diamagnetic substance is one whose
atoms have no permanent magnetic dipole moment.

Consider the figure shown above. We have a diamagnetic substance placed in an external
magnetic field. We see that the field lines get repelled by the material and the field inside the
material is reduced. If we place this substance in a non-uniform magnetic field, it tends to
move from the point of a high electric field to that of a low electric field.

1.1.2 Paramagnetism - Paramagnetism is the magnetic state of an atom with one or even
more unpaired electrons. In a paramagnet, magnetic moments tend to be randomly orientated
due to thermal fluctuations when no magnetic field exists. In an applied magnetic field these
moments start to align parallel to the field such that the magnetization of the material is
proportional to the applied field. This can be illustrated in the diagram below.

2
1.1.3 Ferromagnetism - Ferromagnetism is a physical phenomenon whereby some
materials, such as iron, attract one other aggressively. The magnetic moments in a ferromagnet
have the tendency to become aligned parallel to each other under the influence of a magnetic
field. However, unlike the moments in a paramagnet, these moments will then remain parallel
when a magnetic field is not applied. This can be illustrated in the diagram below.

1.1.4 Anti-ferromagnetism - Anti-ferromagnetism is a kind of magnetism wherein the

magnetic moments of adjacent atoms are antiparallel. Adjacent magnetic moments from the
magnetic ions tend to align anti-parallel to each other without an applied field. In the simplest
case, adjacent magnetic moments are equal in magnitude and opposite therefore there is no
overall magnetization. This can be illustrated in the diagram below.

1.1.5 Ferrimagnetism - Magnetism in which magnetic moments possess oppositional

moments, akin to anti-ferromagnetism is called ferrimagnetism. The aligned magnetic
moments are not of the same size; there is more than one type of magnetic ion. An overall
magnetization is produced but not all the magnetic moments may give a positive contribution
to the overall magnetization. This can be illustrated in the diagram below.

3
1.1.6 Super-paramagnetism- Superparamagnetism is a form of magnetism which
appears in small ferromagnetic or ferrimagnetic nanoparticles. In sufficiently small
nanoparticles, magnetization can randomly flip direction under the influence of temperature.
The typical time between two flips is called the Neel relaxation time’ In the absence of an
external magnetic field, when the time used to measure the magnetization of the nanoparticles
is much longer than the Neel relaxation time, their average value of magnetization appears to
be zero: they are said to be in the super paramagnetic state. In this state, an external magnetic
field is able to magnetize the nanoparticles, similar to a paramagnet. However, their magnetic
susceptibility is much larger than that of paramagnets. Normally, any ferromagnetic or
ferrimagnetic material undergoes a transition to a paramagnetic state above its Curie
temperature. Superparamagnetism is different from this standard transition since it occurs
below the Curie temperature of the material.

Figure 1 Hysteresis loop for magnetic materials

1.2 Nano science and nanotechnology

The prefix ‘Nano’ is referred to a Greek prefix meaning ‘dwarf’ or something very small and
depicts one thousand millionth of a meter (10-9 m). We should distinguish between Nano
science, and nanotechnology. Nano science is the study of structures and molecules on the
scales of nanometre ranging between 1 and 100 nm, and the technology that utilizes it in
practical applications such as devices etc. is called nanotechnology [1]. As a comparison, one
must realize that a single human hair is 60,000 nm thickness and the DNA double helix has a
radius of 1 nm [2]. The development of Nano science can be traced to the time of the Greeks
and Democritus in the 5th century B.C., when scientists considered the question of whether
matter is continuous, and thus infinitely divisible into smaller pieces, or composed of small,
indivisible and indestructible particles, which scientists now call atoms.

4
1.2.1 Nanotechnology in magnetic Material
During recent years, there has been much interest in novel materials in the area of
nanotechnology. Magnetic nanoparticles belong to the group of nanotechnology-based
materials with an impact in fields of analytical chemistry, bio sensing, and Nano medicine. It
has been nearly fifteen years since Pankhurst and colleagues wrote their famous review on
magnetic nanoparticles in biomedicine [3]. More than 50 reviews with the phrase “Magnetic
nanoparticle” in the title have been published in the last decade (according to the Web of
Science). The four applications they have described for magnetic nanoparticles and micro
particles aided in diagnosis and treatment of diseases in the following years.(I) Magnetic
separation of biological entities contributed to the development of diagnostics. (ii) Magnetic
Nano carriers contributed to drug delivery, while (iii) Radio frequency-controlled magnetic
nanoparticles provided a new approach for cancer treatment, in addition to (IV) Magnetic
resonance imaging (MRI) applications. The modification and functionalization of
nanoparticles with various kinds of biomolecules, was already exploited at that time [2, 3].
Nano medicine introduced numerous novel materials for drug delivery and applications in
molecular imaging where accurate detection is dependent on molecular signatures [4].
Magnetic particles are also applicable in the microscopic manipulation of nano- and micro-
sized objects [5]. Applications of magnetic particles ranging from catalysis to drug delivery
and remediation are only limited by their biocompatibility and immunogenicity, both of which
can be controlled by proper layering and coating of particles [6]. To shed some light on the
rapid developments in this field and the future prospects, it is important to deal with the
challenges associated with the processes of design, synthesis and characterization.

1.3 Magnetic Nanomaterial’s

Magnetic nanoparticles are nanomaterial consist of magnetic elements, such as iron, nickel,
cobalt, chromium, manganese, gadolinium, and their chemical compounds. Magnetic
nanoparticles are super paramagnetic because of their Nano scale size, offering great
potentials in a variety of applications in their bare form or coated with a surface coating and
functional groups chosen for specific uses. Especially, ferrite nanoparticles are the most
explored magnetic nanoparticles, which can be greatly increased by clustering of number of
individual super paramagnetic nanoparticles into clusters to form magnetic beads. Magnetic
nanoparticles can be selective attached to a functional molecules and allow transportation to
a targeted location under an external magnetic field from an electromagnet or permanent
magnet.

5
1.3.1 Magnetic Property
The properties of magnetic nanoparticles depend on the synthesis method and chemical
structure. In most cases, the magnetic nanoparticles range from 1 to 100 nm in size and can
display Superparamagnetism. Superparamagnetism is caused by thermal effects that the
thermal fluctuations are strong enough to spontaneously demagnetize a previously saturated
assembly; therefore, these particles have zero coercivity and have no hysteresis. In this state,
an external magnetic field is able to magnetize the nanoparticles with much larger magnetic
susceptibility. When the field is removed, magnetic nanoparticles exhibit no magnetization.
This property can be useful for therapy and targeted drug delivery.

1.3.2 Magneto-caloric Effect

Figure 2 Properties and applications of magnetic materials.

Some magnetic materials "beat" up when they are placed in a magnetic field and cool down
when they are removed from a magnetic field, which is defined as the magneto caloric effect
(MCE) Magnetic nanoparticles provide a promising alternative to conventional bulk materials
because of their particle size-dependent super paramagnetic features. In addition, the large
surface area in magnetic nanoparticles has the potential to provide better heat exchange with
the surrounding environment. By careful design of core-shell structures, it would be possible
to control the heat exchange between the magnetic nanoparticles and the surrounding matrix,
which provide a possible way for improving therapy technologies, such as hyperthermia
Magnetic Nanoparticles have the various applications like magnetic separation, Diagnostic,
Sensors, Drug delivery and therapy.

6
1.4 Ferrites
A ferrite is a ceramic material made by mixing and firing large proportions of iron (III) oxide
(Fe2O3, rust) blended with small proportions of one or more additional metallic elements,
such as strontium, barium, manganese, nickel, and zinc [7]. They are ferrimagnetic, meaning
they can be magnetized or attracted to a magnet. Unlike other ferromagnetic materials, most
ferrites are not electrically conductive, making them useful in applications like magnetic cores
for transformers to suppress eddy currents [4b (Ferrites are super magnetic material widely
used in microwave [8] and electrical industries. They exhibit high electrical resistivity
combine with useful Low temperature NiCuZn ferrite have widely used in inductive
multilayer device because of their relatively high resistivity and good magnetic properties in
high frequency range .

1.4.1 Classification of ferrites

Ferrites are a very well established group of magnetic semiconductor material. Ferrites
are classified by the following categories.

A) On the basis of crystal structure

On the basis of their crystal structure ferrites are of three types namely Hexagonal ferrites,
Garnet and Spinel ferrite. By virtue of their crystal structure they can accommodate variety if
cations at available sites enabling wide variation in electrical and magnetic properties.

a) Spinel ferrites

Figure 3 Spinel Ferrite

Spinel ferrite have general formula MFe2O4 where M stand for divalent metal ion like Ni,
Cu, Zn, and Mg etc. The crystal structure of spinel ferrite possess two interstialsite namely
tetrahedral and octahedral [9].The spinel crystalline in FCC structure with space group of Fd-
3m whose unit cell contain 8 formula unit such that 32 oxygen ion reside at FCC site and 24
metal cation distribution among two kind of non-equivalent interstialsite: 64 tetrahedral and

7
32A octahedral site at witch metal cation are surrounded by 4 and 6 oxygen ion respectively
[10]. Ferrite are well known dielectric material having high resistivity and large vary of
application such as high density storage system, permanent magnet and medical diagnosis
[11]. Spinel ferrite are also being used in magnetic resonance imaging [12]. The advantage of
Ferrite is that they can used in microwave device to low eddy current losses and low
conductivity at high frequency [13].

b) Hexagonal ferrites
The hexagonal Ferrite have general formula MFe12O19 where M is barium strontium
[14].The group of Ferrite which possess hexagonal crystal structure is referred to hexagonal
ferrite. The four type of hexagonal ferrite are indicated as M,W,Y and Z [15].The best known
hexagonal ferrite are those containing barium and cobalt as divalent cation but many
variation of these and hex ferrite containing other cation. Hexagonal ferrite containing
strontium, zinc, nickel and magnesium. The hexagonal ferrite are all ferrimagntic material and
their magnetic properties are linked to their crystalline structure [16].

Figure 4 Hexagonal Ferrite

c) Garnet ferrite Garnet ferrites have the structure of the silicate mineral garnet and the
chemical formula M (Fe5O12) where M is yttrium or a rare-earth ion. In addition to
tetrahedral and octahedral sites, such as those seen in spinel garnets have dodecahedral (12-
coordinated) sites. The net ferrimagnetism is thus a complex result of antiparallel spin
alignment among the three types of sites. Garnets are also magnetically hard [17]

8
 Figure 5 Garnet Ferrite

B) On the basis of magnetism

Due to the persistence of their magnetization, the ferrites are of two types i.e. hard and
soft.

This classification is based on their ability to be magnetized or demagnetized not their ability
to withstand penetration or abrasion. Hard ferrites are difficult to magnetize or demagnetize
whereas soft ferrites are easily magnetized or demagnetized.

Figure 6 Hysteresis curve or B-H curve

9
a) Hard ferrites
Hard ferrite magnets are ceramic magnets that, as you may have guessed, have a high
coercivity. They are still comprised of iron oxide and various metallic elements. Hard ferrite
magnets are types of ceramic magnets. Hard ferrite magnets are less susceptible to
demagnetization than soft ferrite magnets. Hard ferrite magnets include stereo speakers,
electric motors and material handling magnets.

Figure 7 Hard ferrite

b) Soft ferrites
Soft ferrites are not permanent magnets. They carry magnetism (like mild steel) but as soon
as the magnetic field is removed, the magnetism disappears. Soft ferrites are popular as
transformers (to change the voltage from primary to secondary windings). So soft ferrites are
often called transformer ferrites. Soft ferrites exist as toroid’s (rings), C shapes, E-shapes,
curved shapes, etc. Other shapes are possible. They often have performance criteria such as
permeability and inductance.

Figure 8 Soft ferrites

1.5 Applications of ferrites

1) Ferrites are used in thermal sensing switches used in refrigerators, air conditioners,
electronic ovens, etc.
2) The magnetostrictive property of ferrites is utilized in producing ultrasonic waves from a
ferrite rod by the application of an alternating magnetic field.

10
3) The insulating property of ferrites finds their use in electric motors; they are also used as
flat rings for loud speakers, wind screen wiper motors and correction magnets for TV.
4) Some ferrites possess high rectangular hysteresis loop, so they are useful in the
construction of computer memory system for rapid storage and retrieval of digital
information.
5) Mixed ferrites possess high resistivity and good magnetic.

Figure 9 Applications of Ferrite

1.6 Advantages and Disadvantages of Ferrites

▪ Resistivity is high.

▪ Wide range of operating frequencies can be supported.

▪ with high permeability low loss can be achieved.

▪ Different types of material according to applications can be selected.

▪ Flexibility in the choice of core shapes.

▪ Low cost can be achieved.

Disadvantages of soft ferrites are listed below;

▪ Saturation flux density is low.

▪ Thermal conductivity is poor.

▪ Tensile strength is low.

▪ Fragile material.

11
1.7 Aim and Objectives
Scope and Organization of project report
Due to recent advances in nanotechnology and the discovery of innovative methods for their
synthesis, as well as the fascinating features they exhibit, Nano crystalline materials have
acquired a lot of attention and relevance. The purpose of this study is to examine the
correlation between stoichiometric rations in two separate samples, calcination temperature,
doping of divalent metal ion, trivalent metal ion in Mn-Zn ferrites synthesized using the co-
precipitation method. It also aims to investigate the structural, optical, and magnetic properties
of the materials obtained through the application of several known instrumental techniques.

For this study the following work plan was executed

Step 1: Synthesis of Mn0.5Zn0.5Fe2-xO4Cex (where x= 0.00, 0.03, 0.06, 0.09, 0.12 and 0.15)
using CO-Precipitation Method
Step 2: Characterization of powder samples by XRD technique.
Step 3: Grain size measurements and other related structural parameter such as lattice
dimension, bond length, hopping length of powder samples using XRD.

12
 Chapter-2
LITERATURE REVIEW

13
2.1 LITERATURE REVIEW
I] T. Roman ET. All (2019) they are studied, “Structural changes of cerium doped copper
ferrites during sintering process and magneto-electrical properties assessment”. Crystalline
CuCexFe2-xO4 nanoparticles with different rare earth metal content (X= 0.00, 0.03, 0.05, 0.08
and 0.10) were synthesized using a co-precipitation technique that involves a 600°C
calcination treatment. They are characterized it into seven different ways as follows, XRD
analysis, FTIR analysis, SEM and EDX analysis, DLS powder analysis, AFM analysis,
Magnetic behaviour of CuCexFe2-xO4 and dielectric properties- There results comes out For
XRD- The average particle size is, D=126.5nm.

II] K. Geethe, R. Udhaykumar and A. Manikandan (2021) investigated “Cerium

substituted spinel MgFe2O4 ferrite nanoparticles” Spinel MgCexFe2-xO4 (x= 0.0, 0.1, 0.2, 0.3,
0.4, 0.5) nanoparticles was equipped through microwave combustion technique using the
extract of aloe Vera plant as the reducing agent. Impression of Ce3+ substitution on physical-
chemical and photo catalytic characteristics are examined by the techniques, XRD, FTIE,
SEM, TEM and VSM. Cubic spinel structure is ensured by XRD analysis and the crystalline
size was ranges of 16.35 to 24.82 nm. VSM analysis of MgCexFe2-xO4 (x= 0.0, 0.1, 0.2, 0.3,
0.4, 0.5) showed ferromagnetic behaviour.

III] G. Umapathy [Link] (2021) investigated “The Nickel-Zinc (Ni-Zn) ferrites substituted
by cerium (Ce) and having chemicals composition Ni0.5 Zn0.5 Cex Fe2-x O4 (x=0.00, 0.02, 0.04,
0.06, 0.08 and 0.10) were synthesized by combustion method using the organic fuel urea as
reducing agent. Samples were characterized by XRD analysis, FTIR analysis and VSM
analysis. Cubic spinel structure is ensured by XRD analysis and crystalline size was found for
x=0.00 is 45 nm, for x=0.02 is 29 nm, for x=0.04 is 25 nm, for x=0.06 is 20 nm, for x=0.08 is
23 nm and for x=1 is 29 nm. The FTIR spectra of investigated samples recorded in the range
400–4000 cm−1. In general, the spinel ferrite exhibits two prominent absorption bands around
600 and 400 cm−1. In this series, Ni–Zn ferrite with composition Ni0.5Zn0.5Ce0.04Fe1.98O4
has the lowest coercivity values (40.2 kOe) and can be suitable as a soft magnetic material.

IV] Jinhui Tong [Link] (2016) studied the rare earth metal Ce-doped cobalt ferrite samples
CexCo1-xFe2O4 (x = 0.1, 0.3, 0.5) were prepared by the sol–gel auto combustion route. The as-
prepared samples were characterized by XRD analysis, SEM, TEM, etc. Cubic spinel
structure is ensured by XRD analysis and crystalline size was for x=0.1 is 29 nm, for x=0.3 is
23 nm and for x=0.5 is 21 nm. The morphologies of the sample were also characterized by

14
SEM and TEM. The sample features nanoparticles with an irregular morphology and a broad
particle size distribution ranging from 10–20 to 30–50 nm, with a large percentage of small
particles (25–30 nm). The other samples showed similar morphologies, except for different
particle sizes, as calculated from the Scherer equation based on the XRD patterns.

V] C. Viji., Haisel Mathew and [Link] (2017) they studied that, Ce doped Ni-
Zn mixed ferrites with formula CexNi0.6Zn0.4Fe2-xO4 with x varying from x=0.0, 0.02, 0.04,
0.06 are synthesised using sol gel method. Were characterized into XRD analysis, VSM
analysis and FTIR analysis. These results are follows, spherical spinel structure is ensured by
XRD analysis and crystalline size was found for x=0.00 is 16.713 nm, for x=0.02 is 12.124
nm, for x=0.04 is 14.828 nm and for x=0.06 is 13.932 nm. FTIR spectra taken at room
temperature in the wave number range from 400cm-1 to 3500 [Link] distinct broad peaks
are seen in all the spectra. While the high frequency dip around 575cm-1 is the stretching
vibration of metal oxygen bond at the tetrahedral or A site , the lower frequency dip around
400cm-1 corresponds to the metal oxygen bond vibration at octahedral or B site. The magnetic
hysteresis loops recorded at room temp for the samples using VSM. Coercivity Hc (G), for
x=0.00 is 390.26 G, for x=0.02 is 378.49 G, for x=0.04 is 382.46 G and for x=0.06 is 367.91
G.

VI] Mohan Javed [Link] (2022). They investigated that “Integration of Mn-ZnFe2O4 with
S-g-C3N4 for Boosting Spatial Charge Generation and Separation as an Efficient Photo
catalyst” by using co-precipitation method. Were characterized in three different ways, XRD
analysis, FTIR analysis and VSM analysis. Undoped ZnFe2O4 and Mn-doped ZnFe2O4
nanoparticles were observed to be crystalline and included agglomerated, irregular, spherical
nanoparticles with an average size of 20–38 nm. In the wave number range of 4000–450
cm−1, the FTIR spectra of the produced photo catalysts were compared. The observed FTIR
spectrum of ZnFe2O4 confirmed the presence of the M-O bond at 879 cm−1 and the absence
of all functional groups. The peak at 3335 cm−1 was due to the O-H bond stretching while
the peak at 1696 cm−1 was due to the bending of the O-H bond.

VII] M. Mylarappa [Link] (2017) they studied that, Synthesis and characterization of Mn-
ZnFe2 O4 and rGO/Mn-ZnFe2O4 Nano composite from waste batteries for photo catalytic,
electrochemical and thermal studies, by using facile hydrothermal method. The recovered
material was characterized by using X-ray powder diffraction (XRD) to study the particle size

15
and crystallinity. The morphology of the composites was analysed by using Scanning Electron
Microscopy (SEM) and Elements present in the materials were done by Energy Dispersive X
Ray analysis (EDX). The functional groups attached were observed by using Fourier
Transform Infrared Spectrometer (FTIR). The calculated mean crystallite size of the rGO,
Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO` were found to be 14, 27 and 19 nm. FT-IR spectra of
Mn-ZnFe2O4 and Mn-ZnFe2O4/rGO were recorded in the range of 4000-400 cm-1. The
strong and sharp absorption band seemed at 466.7 cm-1 and 430.14 cm-1 is in good agreement
with vibration of Fe-O as characteristic band of spinel ferrite.

VIII] N. Jahan ET. All (2016). A series of polycrystalline Ni–Cr ferrites, with the
composition NiCrxFe2−xO4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0), were synthesized by
conventional solid state ceramic method. The effect of Cr substitution on the structural,
morphological, and magnetic properties of Ni ferrite has been investigated. Were
characterized into XRD analysis, SEM analysis and VSM analysis. The X-ray diffraction
(XRD) patterns of the samples NiCrxFe2−xO4 (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0). The
diffraction peaks confirm the formation of single-phase cubic structure with space group
[Link] parameters like lattice parameters, X-ray density, bulk density, porosity, etc.
were calculated from the XRD data and have been reported earlier. The physical, electrical,
and magnetic properties depend on the microstructure of the ferrite samples. Scanning
electron microscopy (SEM) was used to study the surface morphology and grain size of
NiCrxFe2−xO4 (0.0 ≤ x ≤ 1.0). The magnetic properties of all the samples sintered at 1350
◦ C have been measured using VSM at room temperature with an applied field ±15 kOe.

IX] Atiq Ur Rehman and Mukhtar Ahmad (2020). In this study, a composite of cerium
doped magnesium ferrite (MgCexFe2-xO4, x= 0.1) and banana peel powder was prepared by
hydrothermal method. Crystal structure and phase identification, chemical bonding, and
magnetic properties were characterized by X-ray diffraction (XRD), Fourier transform
infrared (FTIR) and vibrating sample magnetometry (VSM), respectively. XRD results reveal
that the prepared ferrite exhibits single phase face centered cubic (FCC) structure having no
impurity in the sample. Addition of banana peel powder has no effect on the crystal structure.
The values of structural parameters greatly match with the earlier reported values for the same
structure. FTIR results clearly indicate that the prepared ferrite is spinel and have well defined
vibrational and stretching peaks due to different molecules present in the compound.

16
Coercivity values for both ferrite and composite materials are found to be a few hundred
Oersted which confirm the soft magnetic nature of this ferrite.

X] A. Dinesh [Link] (2022). This paper reports the impacts of cerium (Ce) substitution on
morphological, magnetic and structural characteristics of Mn0.5Zn0.5CexFe2-xO4 (x =0.0,
0.3 and 0.5) ferrites nanoparticles (NPs) prepared via sol gel combustion method. The
crystalline structure, magnetic and morphological features were examined by powder X-ray
diffraction, vibrating sample magnetometer and scanning electron microscope analyser
individually. Magnetic hysteresis (M-H) loops of samples were determined to examine the
magnetic properties of synthesized samples. Magnetic measurement shows that samples
exhibit ferromagnetic behaviour at room temperature (RT). The Crystalline size was found
for x=0.0 is 24.31 nm, x=0.3 is 13.28 nm and x=0.5 is 19.12 nm.

17
 Chapter-3
SYNTHESIS METHOD

18
3.1 SYNTHESIS METHOD

Co-Precipitation Method

Co-precipitation method is a classical and perhaps the simplest approach for synthesizing iron
oxide nanoparticles. Basically, this process involves the precipitation of Fe and Fe salt (e.g...
chlorides, sulphates, and nitrates) aqueous solutions by addition of a base (e.g. NaOH). The
size. Morphology, and composition of the as-prepared nanoparticles can be controlled by a
series of experimental parameters, such as the type of precursors, the precursor ratio, the
surface ligand, the reaction temperature, and the pH. To improve the size distribution of the
as-prepared nanoparticles, various surface ligands, such as surfactants, inorganic molecules,
and polymers, have been employed as the stabilizing agents during the precipitation process.

One of the main advantages of this method is that it can directly obtain water-soluble
nanoparticles with high yields in a simple process. Many commercial iron oxide nanoparticle
based MRI contrast agents, such as Feridex, Resovist, and Combidex, are produced by this
method [1]. However, products obtained following this approach sometimes exhibit poor
crystallinity because the reaction temperature is limited by the boiling point of water [2].
Therefore, the saturation magnetization values of iron oxide nanoparticles prepared by this
protocol are typically in the range of 30-50 emu g, which is lower than the 90 emu g of the
bulk value [3].

Co-precipitation reactions involve the formation of simultaneous nucleation, growth,

coarsening, and/or agglomeration processes to take place. Co-precipitation reactions exhibit
the following characteristic stages:

 The products are obtained as an insoluble species in super saturation conditions.

 Nucleation process helps to form a large number of small particles.
 Post nucleation process takes place due to Ostwald ripening processes which lead to
aggregation, dramatically affecting the particle size, shape, morphology, and, with other
applications, properties.
 The super saturation help to induce precipitation at the reaction scale.

XAY+ (aq) +YBX – (aq) = AXBY(S)

19
Advantages of Co-Precipitation Method

1) No daily sludge problem

2) No solid waste

3) Effective and proved technologies

4) No daily use of chemicals

Figure 10. Co-ppt. Method

20
3.4 Procedure
Cerium substituted MnZnCe ferrite having compositional formula Mn0.5Zn0.5Fe2-X O4CeX
was prepared by Co-Precipitation method. .

 The chemicals used AR Grade Magnese Chloride, Zinc Chloride, Ferric Chloride, Cerium
Chloride and Sodium hydroxide.
 Solution-1: Magnese Chloride and Zinc Chloride was dissolved in 50 ml distilled water.
 Solution-II: Ferric chloride and Cerium Chloride was dissolved in 50 ml distilled water.
 Solution -3: Sodium hydroxide was dissolved in 50 ml distilled water.
 Solution-I and Solution-Il both were mixed together and stir continuously on magnetic
stirrer to become a homogeneous solution about 30 minutes and temperature rises up to
solution.
 After that solution of Sodium hydroxide was added to the mixture drop wise until the
required pH (i.e. pH 12) is obtained Continuous Starring.
 After cooling, dark brown precipitate was washed and filtered with the help of what man
filter paper three times with acetone and distilled water respectively.
 Finally, product is obtain on filter paper was dried at 100°C for 3hrs .In hot air oven.
 Then sample was crashed using mortal pestle for 1 hours to get fine powder formed.
 The prepared sample was then calcinated for 6 hours at 750°C.
 After Calcinating again crush sample for 2 hours.
 Then followed by characterization techniques such as XRD, FTIR and VSM

21
Weight chemicals on Mixed solution Stirring of solution
electronic weighing on magnetic stirrer,
balance. MnZn + Fe2O4

Mixed solution of
divalent & trivalent
ions on magnetic
stirrer.

Drying hot air oven Dried sample Crushing for hour

at 100°C for 3 hrs.

22
Washing the Adding of NaOH
precipitate with solution drop wise to
ethanol and water maintain PH at 12

23
Crushing after Calcination using muffle
calcination for 2 hrs. furnace at 750 0C for 6

24
 Chapter-4
CHARACTERISATION

25
4.1 CHARACTERIZATION TECHNIQUES

4.1.1 X-Ray Diffraction (XRD)

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions.
The analysed material is finely ground, homogenized, and average bulk composition is
determined. XRD is a technique used to find out the nature of the materials as crystalline or
amorphous. It will define the quantification of cementations materials. The XRD analysis is
done with an X-ray source of Cu Kα radiation (λ = 1.5406 Å). It will analyse and identify the
unknown crystalline compounds by Brentano method. The different parameters such as scan
step size, collection time, range, X-ray tube voltage and current should be fixed based on the
specimen's requirement analysis. The standard database (JCPDS database) for XRD pattern
is used for phase identification for a large variety of crystalline phases in the concrete
specimens [5].

The powder XRD is the most common and first hand instrument used by solid-state
scientists. X-ray diffraction is a powerful method to investigate the detailed structure,
composition and related properties of nano-materials. This information can be derived from
peak position, intensity and the peak profile. A great advantage of X-ray powder diffraction
is that it requires virtually no sample preparation, in comparison to other techniques.
The sample can be either in the form of smear or compact flat pack or a capillary
and is exposed to monochromatic beam of X-ray and the diffracted beam intensity is
collected in a range of angles (2θ) with respect to the incident beam. The intensity
corresponding to a constructive interference of the diffracted beam from a
crystallographic plane is observed as peak, corresponding to the Bragg angle (θ). In all
other angles a background is obtained. The intensity corresponding to background has several
origins [6].

A powder diffraction pattern contains information on phases present (peak positions),

phase concentrations (peak heights), structure, degree of crystallanity or amorphous
content (background hump) and crystallite size/strain (peak widths/broadening). The
width of the peaks in a particular phase pattern provides an indication of the average
crystallite size. Large crystallites give rise to sharp peaks, while the peak width increases

26
as crystallite size reduces. Crystallite size does not equal the size of the particle, as one
particle can be a conglomerate of several crystallites. Peak broadening also occurs as a
result of variation in d-spacing caused by microstrain. The breadth of the peaks in an
X-ray diffractogram provides a way to determine the average crystallite size, assuming
no lattice strain or defects, through the Debye-Scherrer formula.

D = 0.9λ/ β cos θ

Where t is the thickness of the crystal, λ is the wavelength of the X-rays i.e. 1.054060
A° , β is the full width at half maximum of the diffraction peak, and θ is the Bragg angle
of the peak[6].

Principle of X-ray diffraction

X-ray diffraction is based on constructive interference of monochromatic X-rays and a

crystalline sample. These X-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed toward the sample. The
interaction of the incident rays with the sample produces constructive interference (and a
diffracted ray) when conditions satisfy Bragg's Law.

2d sinθ = n λ

d=λ/2 sinθ

Where‘d’ is interplaner spacing, ‘θ’ is angle of diffraction, ‘^’ is wavelength of

monochromatic x-ray s and ‘n’ is the order of reflection (n=1, 2, 3…).

First order reflection (n=1), the Bragg’s law can be stated as,

2d sinθ=λ

This law relates the wavelength of electromagnetic radiation to the diffraction angle and the
lattice spacing in a crystalline sample. These diffracted X-rays are then detected, processed
and counted. By scanning the sample through a range of 2θangles, all possible diffraction
directions of the lattice should be attained due to the random orientation of the powdered
material. Conversion of the diffraction peaks to d-spacing allows identification of the mineral

27
because each mineral has a set of unique d-spacing. Typically, this is achieved by comparison
of d-spacing with standard reference patterns.

All diffraction methods are based on generation of X-rays in an X-ray tube. These X-rays are
directed at the sample, and the diffracted rays are collected. A key component of all diffraction
is the angle between the incident and diffracted rays. Powder and single crystal diffraction
vary in instrumentation beyond this.

Figure 11 Bragg's Law

X-ray diffraction analysis

Working of X-ray diffract meter

X-ray diffract meters consist of three basic elements: an X-ray tube, a sample holder, and an
X-ray detector-rays are generated in a cathode ray tube by heating a filament to produce
electrons, accelerating the electrons toward a target by applying a voltage, and bombarding
the target material with electrons. When electrons have sufficient energy to dislodge inner
shell electrons of the target material, characteristic X-ray spectra are produced. These spectra
consist of several components, the most common being Kα and Kβ. Kα consists, in part, of
Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as Kα2. The
specific wavelengths are characteristic of the target material (Cu, Fe, Mo, and Cr). Filtering,
by foils or crystal monochrometers, is required to produce monochromatic X-rays needed for
diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a weighted average of

28
the two is used. Copper is the most common target material for single-crystal diffraction, with
Cuα radiation = 1.5418Å. These X-rays are collimated and directed onto the sample. As the
sample and detector are rotated, the intensity of the reflected X-rays is recorded. When the
geometry of the incident X-rays impinging the sample satisfies the Bragg Equation,
constructive interference occurs and a peak in intensity occurs. A detector records and
processes this X-ray signal and converts the signal to a count rate which is then output to a
device such as a printer or computer monitor [6].

Figure 12 X-ray Diffratometer

Application of X-ray diffraction

X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials (e.g. minerals, inorganic compounds). Determination of unknown is critical to
studies material science.

The application are as follows

1. Characterization of crystalline materials

2. identification of fine-grained minerals such as clays and mixed layer clays that are
difficult to determine optically
3. determination of unit cell dimensions
4. Measurement of sample purity.

29
 Chapter-5
CONCLUSION

30
5.2 Conclusion

 Cerium doped Mn Zn ferrite NP’s were successfully synthesized by Co-precipitation

method
 The structural of prepared samples studied from XRD spectra
 The value of crystalline size and lattice parameter is found to be varying indicates the cation
redistribution.
 The doping concentration of cerium affects structural properties and hence creates
applicability in different fields of Nano science
 To study the application of cerium doped Mn Zn ferrites, magnetic properties are to be
investigated.

31
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