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Structural and microstructural characterization

of nanosized Co0.3Zn0.7Fe2O4

Pallab Kumar Bagchi

Examination Roll No: MPHD214025
Class Roll No: 001920702028
MSc Physics, Jadavpur University
Kolkata 700032, West Bengal

Under Supervision Of,

DR. SUVRAJYOTI DEY, Assistant Professor, Department of Physics,
NITMAS, 24 Pargana(S), 743368
PROF. SANJAY KUMAR, Department of Physics, Jadavpur
University, Kolkata 700032
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CERTIFICATE

This is to certify that the project entitled “ Structural and

microstructural characterization of nanosized Co0.3Zn0.7Fe2O4”
submitted by Mr. Pallab Kumar Bagchi , bearing Class roll No
001920702028 of Jadavpur University, Kolkata is an authentic work
carried out by him at the Department of Physics, Jadavpur University
under the guidance of Dr. Suvrajyoti Dey & Prof. Sanjay Kumar. The
matter embodied in this project work has not been submitted earlier
for award of any degree or diploma to the best of our knowledge and
belief.

Jadavpur University
Kolkata 700032

Prof. Sanjay Kumar Dr. Suvrajyoti Dey

Project Supervisor Project Supervisor

Professor Assistant Professor
Department of Physics Department of Physics
Jadavpur University NITMAS,24 Pargana (S)

Date: 27th July, 2021

Kolkata
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ACKNOWLEDGEMENT

I have taken efforts in this project. However, it would not have been
possible without the kind support and help of many individuals. I am
highly indebted to my Project supervisor Dr. Suvrajyoti Dey & Prof.
Sanjay Sarkar for their guidance and constant supervision as well as
for providing necessary information regarding the project & also for
their support in completing the project. I would like to express my
gratitude towards my friend Mr. Debangsu Saha who help me in
completion of this project.
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Contents: Page No

• Introduction…………………………………………………… (5-7)
• Experimental and method……………….……………. (8-11)
• Result……………………………………………………………… (12-18)
• Conclusion………………………………………………………. (19)
• Reference………………………………………………………… (20-21)
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Introduction
In the last few decades, the nanosized spinel ferrites have gathered enormous scientific

attention in the arena of material physics and chemistry for their wide-ranging diverse physio-

chemical properties and also mostly due to their assorted budding efficient applications in

different technological fields like bio sensing (humidity and gas), ferrofluid technology,

magnetic resonance imaging (MRI), microwave and radio frequency devices, magnetic storage

devices, targeted drug delivery, hyperthermia treatment to treat tumour and cancer etc [1-6]. In

addition to these, spinel ferrites displays spectacular nanoscale magnetic properties which are

remarkably dissimilar compared to their bulk counterparts. Some nanoscale magnetic

properties of ferrites like superparamagnetism, collective magnetic excitation, spin canting

effect, spin glass like behaviour require substantial attention both from the viewpoint of

fundamental physics and to facilitate these finding for their fruitful technological applications

[7 – 10].

It is well known that spinel ferrite possesses face centred cubic (fcc) crystal structure

of fd-3m symmetry and has AB2O4 type formula unit, where A and B denotes tetrahedral and

octahedral sites of the crystal lattice [11, 12]. The most general formula for ferrite is MFe2O4,

where M designates generally divalent transition metal oxides like Mn, Zn, Mg, Co, Ni etc.

The crystal structure is comprised of eight formula units of MFe2O4 in one unit cell. In each

formula unit there are eight tetrahedral and four octahedral sites are present. 32 oxygen ions

generates a face centred cubic lattice where two types of crystallographic sites are present,

tetrahedral (A) site surrounded by four oxygen ions along with octahedral [B] sites surrounded

by eight oxygen ions. If we consider the unit cell, then 8 of 64 available (A) sites and 16 out of

32 available [B] sites are occupied [1]. Depending upon the position and distribution of the (A)

and [B] site cations, ferrites are classified into three groups: (1) Normal spinel, (2) Inverse

spinel and (3) Mixed spinel [5, 11]. The site occupation of the cations mainly depends upon
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electrostatic contribution towards lattice energy, charge of the cation, radii (size) of the cation,

effect of the crystal field. Fe ions can occupy both (A) and [B] sites. If the Fe ions are present

completely in [B] site, the ferrite is termed as normal spinel (ZnFe2O4), whereas the ferrites

with Fe ions distributed equally between (A) and [B] site is called inverse spinel (NiFe2O4,

CoFe2O4). In case of a mixed spinel structure the divalent Me2+ cation and Fe3+ can randomly

occupy (A) and [B] sites [5, 11].

Fig. 1. Crystal structure of spinel ferrites [13]

Recent studies indicate that the nanoscale magnetic properties of spinel ferrites are strongly

reliant on the variety of cations and their comparative distribution among the tetrahedral (A)

and the octahedral [B] sites of the spinel lattice [5]. It has been shown that the exchange

interactions in ferrites is intermediated by the oxygen ions. In general, the exchange integrals

JAA, JBB and JAB are negative and the antiferromagnetic A-O-B interaction (JAB) interaction is

much stronger than the A-O-A (JAA) and B-O-B (JBB) interactions which causes the spins of

(A) and [B] sublattice aligned and frustrated [5, 14, 15]. As a consequence, the spins of the

cations of dissimilar sublattices becomes anti-parallel in nature. In this connection it may be

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inferred that if all the cations possess a magnetic dipole moment, we can expect ferrimagnetic

ordering for such systems [5, 14, 15]. If one can induce structural disorder by the introduction

of nonmagnetic ions in the lattice, it may lead to frustration in the system and result in spin

disorder or spin glass like behaviour in the system. In this background the study of structural

and microstructural properties of magnetically diluted substituted ferrites appears to be

interesting.

As discussed above, CoFe2O4 is inverse spinel in nature and due to its favourable atomic

size and charge distribution inside an octahedral crystal field Co+2 ions only occupy the [B]

sites and the Fe3+ ions are equally distributed between (A) and [B] sites of the crystal lattice

[5]. The structural formula of CoFe2O4 is (Fe3+)A[Co2+Fe3+]BO4. It is evident from the structural

formula that the FeA-O-FeB interaction is much strong in CoFe2O4 and it is ferromagnetic in

nature below 790 K (TN). In contrary, ZnFe2O4 is normal spinel in nature and all the Fe3+ ions

reside in [B] site [5]. The structural formula of ZnFe2O4 is (Zn2+)A[Fe3+Fe3+]BO4 which reveals

that the FeA-O-FeB interaction is not operative here. The magnetic ordering temperature (TN) is

only ~ 9 K for ZnFe2O4. If we substitute Co2+ cations in CoFe2O4 by nonmagnetic Zn2+ cations,

it will promote Fe3+ ions to migrate from (A) to [B] site and surely decrease the FeA-O-FeB

interaction [5]. The equilibrium cation distribution among the (A) and [B] sites of Co-Zn ferrite

is given by (Zn1-xFex)A[CoxFe2-x]B O4. However, the magnetic property of nanosized Co-Zn

ferrite is strongly influenced by structural and microstructural parameters (crystallite size,

shape, lattice strain), choice of magnetic cations, relative cation distribution among the (A) and

[B] sites, spin canting effect etc which are also dependent upon synthesis technique adapted

and synthesis parameters. In this connection the synthesis and study of structural and

microstructural of nanometric Co0.3Zn0.7Fe2O4 appears to be promising.

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Experimental and method

Synthesis of Co0.3Zn0.7Fe2O4 nanoparticle system:

Initially, the nanosized Co0.3Zn0.7Fe2O4 was synthesized by adapting the standard chemical

coprecipitation method. We have used Cobalt (II) chloride hexahydrate [CoCl2. 6H2O], Zinc

(II) sulphate heptahydrate [ZnSO4.7H2O] and Iron(III) nitrate nonahydrate [Fe(NO3)3.9H2O]

of purity more than 99.99% as precursor. All the reagents have been purchased from Sigma-

Aldrich and used without further purification. The aqueous solution of the above mentioned

salts in proper molar concentration required for Co0.3Zn0.7Fe2O4 were taken in a beaker and

mixed together through vigorous stirring using a magnetic stirrer. In a separate beaker an

aqueous solution of NaOH having pH ~ 10 was prepared. The NaOH solution was poured into

the mixture of the salt solution using a burette under vigorous stirring. The pH of the solution

was maintained at about 10 during the whole reaction period by measuring the pH through a

pH meter and adding NaOH solution through the burette as and when required. After

completion of the reaction a deep brown precipitate was obtained which was collected by

careful filtration and washed with deionized water several times using Centrifuge instrument.

Afterward, the collected sample was dried in vacuum oven at room temperature. Next the

sample was sintered at 500°C for 8 h for complete phase formation. After that, the sintered

powder of the precursor was manually grinded in an agate mortar for 1h and then it was ball

milled at room temperature (300 K) for 12 h in a Fritsch Planetary Mono Mill “pulverisette6”

using tungsten carbide vials and balls of mass 1.0 g. The ball to powder mass ratio was 20:1

and the rotating speed of the mill was maintained at 350 rpm during the experiment. The ball

mill was paused for 5 min after every 1 h, then the vial was opened and its inner wall was

scratched with a spatula to remove the samples which got attached with the wall during milling.
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Fig. 2. Fritsch Planetary Mono Mill “pulverisette6” [16]

Powder X Ray Diffraction

Powder X Ray diffraction (PXRD) is the most widely used diffraction method to determine the

structure of crystalline solids. In PXRD the diffraction pattern is obtained from powdered

material rather than a crystal. The powder of the sample is prepared by crushing the

polycrystalline material. The experimental arrangement consists of a cylindrical camera, called

the Debye-Scherrer camera, whose length is small as compared to the diameter. The X ray

enter the camera through the collimator and strike the powdered sample. Since the specimen

contains a large number of small crystallites (1012 in 1 mm3 of powder sample) with random

orientation, almost all the θ and d values are available. The diffraction takes place for those

values of d and θ which satisfy the Bragg’s condition, i.e., 2d sinθ = nλ , λ being a constant in

this case. Also, since for a particular value of the angle of incidence θ, numerous orientations

of a particular set of planes are possible, the diffracted ray corresponding to fixed values of θ

and d lie on a surface of a cone with its apex at the sample and the semiverticle angle equal to

2θ. A radiation detector records the various reflected lines as a function of angle 2θ [17, 18].
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The PXRD pattern of this sample was recorded by Bruker D8 Advanced Diffractometer using

Cu Kα (λ= 1.5406 °A) radiation. The data was collected at room temperature (21 degree C)

over the range of 2θ = 15 – 80° with step size and counting time of 0.0199° and 5 s per step,

respectively. The voltage and current of the x-ray generator were set at 35 kV and 35 mA,

respectively.

Fig. 3. X ray diffraction from lattice plane

Fig. 4. Powder X Ray Diffractometer

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Transmission electron microscope

In transmission electron microscopy electron beam is used to produce the image of sample.

Compared to optical microscope which magnifying power is up to 2000 times, it has

magnifying power upto 50 million times. Since a high energy electron beam has wavelength

very less than optical wavelength, it can resolve two very close point, actually it can resolve

two atoms (few nm) in a crystal. So, it is a very significant tool to know the microstructure of

a crystal. A beam of electrons is transmitted through a sample, creating an image that details a

sample’s morphology, composition, and crystal structure. Samples must be incredibly thin,

often less than 150 nm thick, to allow electrons to pass through them. After the transmission

of the electrons through the sample, they arrive at a detector below and a 2-D image is created.

The details provided are at the atomic level, the highest resolution of any electron microscope.

The high resolution transmission electron (HRTEM) micrograph of the present sample have

been recorded by using JEOL 2100 HRTEM.

Fig. 5. Transmission Electron Microscope

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Result and Discussion:

PXRD Data Analysis
The PXRD pattern of bulk Co0.3Zn0.7Fe2O4 synthesized by standard ceramic route is provided

in Figure 6 to compare with the PXRD pattern of nanosized Co0.3Zn0.7Fe2O4 (Figure 7). It is

evident from the PXRD pattern of the nanosized Co0.3Zn0.7Fe2O4 that only the characteristic

diffraction peaks ascribing to the spinel crystal structure are present and no additional peaks

corresponding to any impurity phase was noticed. The PXRD data is in good accord with the

JCPDS database of ZnFe2O4 and CoFe2O4 systems (JCPDS No. 89-1012 and 22-1086 for

ZnFe2O4 and CoFe2O4, respectively) [19]. The peaks were identified and indexed by using the

reports available in literature [19 – 22]. Thus the primary PXRD study indicates that the sample

under investigation is single phase, nanosized cubic spinel Co-Zn ferrite. The substantial

broadening along with the diminished intensity of the Bragg peaks of nanosized samples

compared to it’s bulk counterpart is the manifestation of nanometric size, structural disorder,

amorphous character of the surface and large internal strain among the lattice planes [24]. The

PXRD pattern of nanosized Co0.3Zn0.7Fe2O4 have been fitted by using Origin software adopting

Lorentzian profile to obtain the peak positions and full width at half maxima of the individual

peaks. The crystallographic ‘d’ values corresponding to different lattice planes have been

determined by using Bragg’s law. From the Bragg’s law we know

𝟐𝟐𝟐𝟐 𝐬𝐬𝐬𝐬𝐬𝐬 𝜽𝜽 = 𝒏𝒏𝒏𝒏

Where, λ is the wavelength of the incident X-ray (here Cu Kα (λ= 1.5406 °A)), θ is the position

of a particular peak (in radian), n is the order of diffraction (here n = 1) and d is the interplanar

spacing.

𝒏𝒏 𝝀𝝀
𝒅𝒅 =
𝟐𝟐 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔
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Fig. 6. PXRD pattern of bulk Co0.3Zn0.7Fe2O4.

Fig. 7. PXRD pattern of nanosized Co0.3Zn0.7Fe2O4.

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Table for the calculation of crystallographic ‘d’ value:

Peak 2θ (degree) θ(radian) Sin θ d spacing

(nm)
hkl

220 30.07898 0.262488618 0.25936 0.296857546

311 35.40919 0.309003475 030396 0.253296953

400 42.99954 0.375241775 0.36632 0.210178792

422 53.42276 0.466201529 0.44929 0.171369548

511 56.90787 0.496614851 0.47623 0.161674192

440 62.49575 0.545378303 0.51851 0.148493985

In addition to this, the average crystallite size and residual strain have been estimated by using

Williamson-Hall plot [8, 25]. In the PXRD data of the sample the peak broadening (βT) is

associated with the combined effect of crystallite size (βD) and microstrain (βε).

From the Scherer equation we know that,

𝑘𝑘𝑘𝑘
𝐷𝐷 =
𝛽𝛽𝐷𝐷 cos 𝜃𝜃

𝑘𝑘𝑘𝑘
𝛽𝛽𝐷𝐷 =
𝐷𝐷 cos 𝜃𝜃

Where, βD is the full width at half maxima (FWHM) of the peaks, k = 0.9 is the shape factor,

λ is the wavelength of the incident X-ray (here Cu Kα (λ= 1.5406 °A)), θ is the position of a

particular peak (in radian).

Similarly, the XRD peak broadening due to the microstrain is given by,

𝛽𝛽𝜀𝜀 = 4𝜖𝜖 tan 𝜃𝜃

The total broadening is given by,

βT = 𝛽𝛽𝐷𝐷 + 𝛽𝛽𝜀𝜀
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Thus putting the values of 𝛽𝛽𝐷𝐷 𝑎𝑎𝑎𝑎𝑎𝑎 𝛽𝛽𝜀𝜀 in this equation we have,

𝑘𝑘𝑘𝑘
𝛽𝛽𝑇𝑇 = + 4𝜖𝜖 tan 𝜃𝜃
𝐷𝐷 cos 𝜃𝜃

Multiplying both side of the equation with cos θ we get,

𝒌𝒌𝒌𝒌
𝜷𝜷𝑻𝑻 𝒄𝒄𝒄𝒄𝒄𝒄 𝜽𝜽 = + 𝝐𝝐 𝟒𝟒 𝒔𝒔𝒔𝒔𝒔𝒔 𝜽𝜽
𝑫𝑫

Now if we plot 𝛽𝛽𝑇𝑇 cos 𝜃𝜃 vs. 4 sin 𝜃𝜃 in a graph, we shall obtain a straight line which will have

Slope = ε and

𝒌𝒌𝒌𝒌
Intercept in the y axis =
𝑫𝑫

By obtaining the slope we can easily determine the microstrain and by using the value of k =

0.9 for the shape factor and λ= 1.5406 Å for the wavelength of the incident Cu Kα X-ray we

can easily obtain average crystallite size.

Table for the calculation of Williamson-Hall plot:

Peak 2θ(degree) β or θ (radian) β (radian) 4 sinθ β cosθ

hkl FWHM

(degree)

220 30.07898 0.61341 0.262488618 0.010706024 1.037938917 0.592398997

311 35.40919 0.76434 0.309003475 0.01334025 1.216437846 0.728138637

400 42.99954 0.77868 0.375241775 0.01359053 1.465989967 0.724498697

422 53.42276 0.84412 0.466201529 0.014732673 1.797985719 0.75403731

511 56.90787 0.93664 0.496614851 0.016347452 1.905808198 0.823494317

440 62.49575 0.97093 0.545378303 0.016945925 2.074966202 0.830078263

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Fig. 8. Williamson-Hall plot of the PXRD data of nanosized Co0.3Zn0.7Fe2O4

Now from the Williamson-Hall plot we have the value of the intercept = 0.00764 and the value

of the slope of the straight line = 0.00335

𝒌𝒌𝒌𝒌
Thus using the equation Intercept in the y axis =
𝑫𝑫

Slope = ε and

The value of average crystallite size = 18.955 nm and the value of the microstrain is = 0.00335
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High resolution transmission electron microscopic (HRTEM)

study
The HRTEM images of nanosized Co0.3Zn0.7Fe2O4 is shown below. It is well known that the

magnetic nanoparticles have tendency to form agglomerate and it becomes difficult to capture

the TEM image of the individual particles. To avoid this difficulty we have adopted a special

technique in TEM sample preparation [24]. First of all small amount of sample was thoroughly

dispersed in ethanol through vigorous ultrasonication. Then the carbon coated copper grid was

placed over a spin coating unit which is rotating with 300 rpm speed. Then a small drop of

sample dispersed in ethanol was poured on the grid and then the grid was dried. The overview

of the TEM images suggest that this method was capable of preventing the agglomeration. The

close inspection of the TEM images reveals that the individual particles are of assorted size

with roughly spherical shape and the size ranges between 10-35 nm. The particle size

distribution obtained by measuring the diameters of 240 individual particles through ImageJ

software has been shown in the histogram. The histogram has been fitted by lognormal

distribution function and the average particle size appears to be 19 nm.

Fig. 9. HRTEM images of nanosized Co0.3Zn0.7Fe2O4

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Fig. 10. histogram of particle count and lognormal curve

Conclusion
In this work, I have synthesized nanosized Co0.3Zn0.7Fe2O4 by coprecipitation method

following high energy ball milling. The structural and microstructural characterization of the

sample have been performed by powder x-ray diffraction (PXRD) and high resolution

transmission electron microscopic (HRTEM) techniques. The PXRD study indicates that the

sample under investigation is single phase, nanosized, spinel Co0.3Zn0.7Fe2O4 ferrite. The

crystallographic ‘d’ values have been estimated by fitting the PXRD pattern using Lorentzian

profile. The Williamson-hall plot has been used to obtain the average crystallite size and

microstrain of the sample. The values of average crystallite size and microstarin are 18.955 nm

and 0.00335, respectively. Further the particle size was estimated by measuring the individual

particles in the TEM images. The particle size distribution histogram has been fitted with

lognormal distribution curve and the average particle size appears to be 19 nm, which is in

good accord with the PXRD study.

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