Accepted Manuscript

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Surfactant assisted synthesis of rare earth Dy substituted MnFe2O4 nanoparticles

Mirza Mahmood Baig, Muhammad Asif Yousuf, Muhammad Farooq Warsi, Philips
Olaleye Agboola, Muhammad Sher, Imran Shakir

PII: S0272-8842(19)31504-4
DOI: https://doi.org/10.1016/j.ceramint.2019.06.020
Reference: CERI 21829

To appear in: Ceramics International

Received Date: 25 May 2019

Revised Date: 2 June 2019
Accepted Date: 3 June 2019

Please cite this article as: M.M. Baig, M.A. Yousuf, M.F. Warsi, P.O. Agboola, M. Sher, I. Shakir,
3+
Surfactant assisted synthesis of rare earth Dy substituted MnFe2O4 nanoparticles, Ceramics
International (2019), doi: https://doi.org/10.1016/j.ceramint.2019.06.020.

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 ACCEPTED MANUSCRIPT

Surfactant Assisted Synthesis of Rare Earth Dy3+ Substituted MnFe2O4 Nanoparticles

Mirza Mahmood Baig*a, Muhammad Asif Yousufa, Muhammad Farooq Warsia, Philips Olaleye
Agboolab, Muhammad Sherc, Imran Shakir*d
a
Department of Chemistry, The Islamia University of Bahawalpur-63100, Bahawalpur-Pakistan

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b
College of Engineering Al-Muzahmia Branch, King Saud University, PO-BOX 800, Riyadh
11421, Saudi Arabia

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c
Department of Chemistry, The University of Sargodha, Sargodha-40100, Pakistan
d
Sustainable Energy Technologies (SET) center, College of Engineering, King Saud University,

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PO-BOX 800, Riyadh 11421, Saudi Arabia

Corresponding author: mahmood.baig@iub.edu.pk, mshakir@ksu.edu.sa

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Abstract
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In this study, we substituted the magnetic Fe3+ ions with highly paramagnetic rare earth Dy3+
cations in MnFe2O4 spinel ferrite nanoparticles to investigate the physical, structural, spectral
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and electrical properties in detail. Dysprosium substituted inverse spinel ferrite nanoparticles
(DyxMnFe2-xO4) (0≤ x ≥0.16) were prepared via facile optimized wet chemical approach i.e.
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micro-emulsion route. Substituted and unsubstituted manganese ferrite nanoparticles were

annealed at 400 °C for 4 hours under vacuum. X-ray diffraction (XRD) analysis proved the
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spinel structure of all compositions of DyxMnFe2-xO4 nanoparticles. Various physical parameters

were calculated from XRD data. Quantitative measurements of cations distribution were carried
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out to estimate the distribution of divalent metal cations (Mn2+) and trivalent metal cations (Fe3+
and Dy3+) between A-sites (tetrahedral) and B-sites (octahedral). Oxygen parameter ‘u’ was
calculated to study the displacement of oxygen ions in tetrahedral sites along (111) direction.
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Fourier transform infrared spectra (FTIR) were recorded to study the two significant absorption
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bands corresponding to A-site and B-site. Scanning electron microscopic (SEM) analysis was
carried out to study the morphology of DyxMnFe2-xO4 nanoparticles. After structural and
morphological investigations, all compositions of DyxMnFe2-xO4 nanoparticles were subjected to
dielectric parameters measurements. The dielectric parameters like dielectric constant (real and
imaginary part) and tangent loss were investigated as a function of frequency from 1 MHz to 3
GHz at room temperature.
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Key Words: Inverse Spinel; DyxMnFe2-xO4; Reverse Microemulsion; XRD; Cations

Distribution; Dielectric Parameters.

1. Introduction

Modern society is demanding multifunctional smart materials. Materials is a broad research field

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that has attracted the scientists of almost all disciplines. Engineers, chemists and physicists are
three major stakeholders. Since last few decades, the nanotechnology and hence

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nanotechnologists also playing their role to develop and fabricate the smart multifunctional
materials / nanomaterials. In the subject of nanotechnology and nanoscience, the researchers

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prepare the materials with required properties by tailoring the size of the particles / crystallites or
and grains. The materials can be classified into two major classes based on their magnetic

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properties. These are magnetic materials and non-magnetic materials. Magnetic materials such
as ferrites have attracted the researchers owing to their special electrical and magnetic properties.
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Ferrites have many sub-classes depending on their magnetic strength, crystal structure and type.
For example, generally, ferrites have three classes. These are (i) spinel ferrites (ii) hexagonal
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ferrites and (iii) Garnets. Manganese ferrite is one of the most attractive spinel ferrites. The
general formula of spinel ferrites is AB2O4. In this formula “A” is any divalent metal cation (like
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Ca2+, Mn2+, Mg2+, Cu2+, Co2+ etc) and “B” is trivalent metal cations (like Fe3+). spinel ferrites
have versatile applications ranging from medical imaging to electronics industry. Nano-ferrites
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have been deeply studied due to their saturation magnetization, remarkable high electrical
resistivity and high permeability [1-3]. The materials possessing high magnetic permeability, low
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eddy current losses and good mechanical behavior are required for high frequency transformers
and high-pace recording media and microwave devices fabrication [4-5]. Manganese ferrite is a
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type of soft magnetic materials and attains significance weightage in nanotechnology due to their
excellent magnetic and electrical properties. Owing to its higher magnetic susceptibility,
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manganese ferrite is preferred as compared to other spinel ferrites like CoFe2O4 and NiFe2O4 for
many advanced technological applications [7]. Superior biocompatibility of these ferrites as
compared to nickel ferrite, cobalt ferrite, magnetite and hematite make it vital for MRI based
explorations as MRI contrast agents [8]. Due to their low dielectric losses and high resistivity,
there does not exist any known material like MnFe2O4 with such wide potential range in
electronic applications like power generation, power conversion, remediation of organic
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pollutants, hyperthermia treatment, microwave heating etc [9-10]. Various properties of ferrites
are affected by synthetic methods, stoichiometry and nature of substituents or and dopants [11].

A small rare earth ion substitution at octahedral B-site causes 3d-4f coupling which relates to
magneto-crystalline anisotropy and high magnetostriction for low temperatures hence attributing

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the enhanced electrical and magnetic properties [12-14]. Rare earth ions may also responsible for
enhanced permeability and resistivity of ferrites along with densification [15]. Electrical and

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magnetic properties of MnFe2O4 can be improved drastically by substituting rare earth ions. Rare
earth ions contain desirable magnetic moment, particular site preference and good ionic stability.

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The level of modification regarding enhancement of electrical and magnetic properties of
MnFe2O4 to some extent depend upon the substituting materials. For this purpose, rare earth
chemical elements such as La, Ce, Dy, Pr, Nd, Er etc. are the best choices because of their site

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preferences, electronic configuration and especially larger ionic radius [16-18].
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Due to the unpaired electrons in the 4f sub shell present in the rare earth (RE) ions when
substitute in manganese based spinel ferrite system may change their intrinsic electrical and
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magnetic properties by the occurrence of 4f-3d spin-orbit (L-S) coupling of electrons. Therefore,
the researchers prefer RE elements as compared to transition elements for substitution [19]. Rare
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earth ions like Dy3+ with larger ionic radius when substituted is supposed to distort the structure
which induces micro strain and electrical properties get modified [20]. The 3d-4f (L-S) coupling
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improves the ordering of magnetic moment, which changes the net magnetization [21]. A brief
review of recent literature reports on rare earth substituted spinel ferrites including MnFe2O4 is
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described in the following paragraph.

Rezlescu et al. reported the impact of rare earth metallic ions (Dy, Gd,
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Yb, Sm) on various physical and structural properties of Lithium-Zinc ferrite. The studies
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showed the suppression in grain growth, lowering of Curie temperature and enhancement in
electrical resistivity [23]. E. Ateia et al. worked on the substitution of Fe3+ ions by rare earth ions
like Dy3+, Sm3+, Gd3+, La3+ and Ce3+) and found that these small substitutions in the Mn-Zn
ferrites affect the electrical and magnetic features of doped ferrites and categorized as p-type
semiconductor. Their good electrical and magnetic properties make them suitable for use in
applications of high frequency devices fabrication [24]. Among f-block elements, dysprosium
(Dy) is one of the rare earth elements, which possess high magnetic moment along with high
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electrical resistivity. Therefore, to meet the need of highly resistive material with high dielectric
constant values, we aim to investigate the substitution of Fe3+ ions by Dy3+ ions in manganese
ferrite system using micro-emulsion (size and solubility controlled) method which has never
been studied previously, to the best of our knowledge. Further, it is important to mention that we
have used the optimized conditions of micro-emulsion route for synthesis of all compositions of

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DyxMnFe2-xO4 nanoparticles reported in our previous communication [25].

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2 Experimental Work

2.1 Chemicals

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The synthesis of substituted and unsubstituted MnFe2O4 spinel nanoparticles was carried out
using the same procedure as reported earlier in our previous communication [25]. All precursors

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were of analytical grade (extra pure). We have not carried out any purification of the received
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chemicals / precursors. These chemicals are Iron (III) Nitrate Nona hydrate (Fe (NO3)3. 9H2O,
>98%, Carl Roth GmbH), Manganese acetate (Mn(CH3COO)2.4H2O, 98 %, Daejung ),
Dysprosium Nitrate (Dy(NO3)3·xH2O), 99 %, Sigma Aldrich), Paraffin oil, Triton X-100
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(C34H62O11, Merck); 1-butanol (C4H9OH, ˃98%, Merck); Sodium hydroxide (NaOH, 99%,
affymetrix) and Ethanol (C2H5OH, Merck).
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2.2 Synthesis of DyxMnFe2-xO4 Nanoparticles

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Unsubstituted and Dy3+ substituted manganese ferrite (DyxMnFe2-xO4, x= 0.0, 0.01, 0.02, 0.04,
0.08, 0.16) nanoparticles were synthesized via optimized wet chemical approach [25]. This
method involved the use of a surfactant and a co-surfactant. The paraffin oil was used as oil
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phase. Freshly prepared metal salts solutions (Mn2+, Fe3+ and Dy3+) were used in this synthetic
work. All prepared reaction mixtures according to stoichiometric ratios were heated at 60 °C for
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10 minutes. Subsequently, micro-emulsion (TritonX-100/1-butanol/Paraffin) was added in each

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reaction mixture. pH of all prepared reaction mixtures were maintained at 11 by sodium

hydroxide (1 M) solution. The stirring of the solutions was carried out for one and half hour. The
reaction mixtures were placed on bench for settling down the precipitates, which were washed
with deionized water several times. The obtained precipitates dried in oven at 150 °C. The
annealing of the grinded precipitates was done at 400 °C for 4 hour under vacuum. The possible
suggested reactions taking place during synthesis of manganese ferrite particles is give as
follows:
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Mn2+ + 2OH- → Mn(OH)2 (1)

Fe3+ + OH- → Fe(OH) 3 (2)

Dy3+ + OH- →Dy(OH) 3 (3)

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Mn (OH) 2 + Fe (OH) 3 + Dy(OH) 3 Dyx MnFe2-xO4 (4)

3. Results and Discussion

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3.1 Thermogravimeteric Analysis (TGA)

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To find out the annealing temperature, TGA/DSC analysis of un-annealed sample of MnFe2O4
(Dy-0) was carried out and has already been discussed in detail in our previous papers [25-26].

3.2 XRD Results

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XRD patterns are used to investigate the phase and purity of the prepared solid-state crystalline
materials. The XRD patterns of unsubstituted and Dy3+ substituted MnFe2-xO4 nanoparticles were
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measured at room temperature. The two-theta range was kept from 15° to 80°. All these patterns
are shown in Figure 1 (a).
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The single-phase cubic structure was confirmed by XRD data and the patterns were matched
with data card JCPDS#10-0319. All planes (220), (311), (222), (400), (422), (511) represent the
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cubic spinel structure of Mn-ferrites for all compositions of DyxMnFe2-xO4 nanoparticles.

The lattice constant (a) values for all compositions of DyxMnFe2-xO4 nanoparticles were
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calculated using equation 3.1.

(5)
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In this equation, the “d” is interplaner spacing and calculated from Bragg’s equation (nλ=
2dsinϑ) , and “h”, “k”, “l” are the miller indices .
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The size of crystallites of all compositions of DyxMnFe2-xO4 nanoparticles was determined by

following mathematical equation.
(6)

In this equation, the “λ” is the wavelength of X-rays used (1.5405 Å) and β is the full width at
half maximum. The value of full width half maximum (FWHM) was taken from the most intense
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peak with hkl value (311). X-ray density (dx) and bulk density (db) using Archimede principle
and percentage porosity (P) was calculated by using following equations respectively [26].

(7)

(8)

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(9)

In above equations, the “M”, represent the molecular weight of sample, “N” is Avogadro

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number and “a” is lattice constant, “m” is the mass, “r” is the radius, “h” is the thickness of
sample.

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The prominent effect of Dy3+ substitution has noted in two main observations of XRD results. In
general, lattice constant increases while crystallite size decreases as shown in Figure 1 (b) and

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Table 1. On substituting Dy3+ ions, the lattice constant increased. This slight increase in lattice
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constant on substitution attributed to displacing the small sized transition metal ion with large
sized rare earth ion. The slight decrease in lattice constant on substitution attributed to the
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occupancy of the rare earth ions in the lattice sites improperly. As the ionic radii of Dy3+ ions
(0.104 nm) is larger than the ionic radii (0.067 nm) of Fe3+ ion. Similar to other rare earth ions
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from the lanthanide series, it also occupies B- site (octahedral). Therefore, lattice parameter ‘a’
of the substituted MnFe2O4 increases which causes distortion in the lattice [27].
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The peak shifting confirmed the substitution as shown in Figure 1 (c). The (311) intense peak
shifts to both directions i.e. higher 2 theta degrees (positive shift) and lower 2 theta degrees
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(negative shift) corresponding to decrease and increase in interplanar spacing (311) respectively
which confirms the Dy3+ ions loading. Moreover, during crystal growth the higher binding
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energy of Dy3+-O2- as compared to Fe3+-O2- entail more enthalpy for the formation of Dy3+-O2-
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bond which consequences smaller crystallite size. Decrease in crystallite size shows reduction in
degree of crystallinity [28].

The formation of DyFeO3 (minute secondary phase) appeared at the crystal boundaries of
Dy-3 to Dy-5 matched with JCPDS# 00-019-0433 which may hinders the crystal growth and
responsible for decrease in crystallite size. As the bond energy of Dy3+-O2- is high as compared
to the bond Fe3+-O2- so to introduce Dy3+ into lattice to form Dy3+-O2- bond, high amount of
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energy is required relatively. It shows that the Dy-MnFe2O4 system is more thermally stable as
MnFe2O4 system [29].
It is observed from Table 1 that, the X-ray density increased with increase in Dy3+ ions
concentration (Table 1). On the other hand, bulk density is smaller than X-ray density that is
normal behavior and observed with formation of pores during synthesis and sintering process.

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Thickness of pellets may affect the bulk density calculations . The porosity of DyxMnFe2-xO4
nanoparticles was 40-50 % that indicated the prepared samples are quite porous and may find

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potential applications in adsorption phenomenon.

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3.3 Rare earth ions solubility and synthesis method

Synthesis methodology largely influences the solubility of rare earth ions, and to control the

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appearance of secondary phases. These secondary phases are generally rare earth oxides and
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ortho-ferrites. Solubility limit also depends on post heat treatment. As our host material, the
MnFe2O4 is very sensitive to heat treatment so the post heat treatment of manganese ferrite
usually produces the secondary phase that may affect its properties. The reverse
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micro-emulsion method has proved to be the best method to control size of particles, shape or
geometry, morphology, surface area and especially the solubility of these larger radii elements.
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At very low temperature, this technique favors single-phase creation due to homogeneous
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integration of primary precursor particles. The mostly observed complications in all discussed
methods at elevated temperature are coarsening and aggregation of particles along with
appearance of secondary phase.
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To synthesize single-phase, de-agglomerated, porous and monodisperse particles, micro-

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emulsion technique is the most useful technique. Therefore, we opted numerous routes to
synthesize the single phase, low cost, monodisperse, porous, environmental friendly and nano-
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sized manganese ferrite and finally succeeded in finding a new and cheap route i.e. water in
paraffin oil (micro-emulsion method) [31-35].

3.4 Cations Distribution Calculations between Tetrahedral and Octahedral Sites

It is very important to understand the cations distribution for study of sensitive site occupancy of
ferrites. The ionic radii, jump length, bond length of A and B site and oxygen parameters are
calculated for Dy3+ substituted Mn-ferrite nanoparticles. The ionic radii “rA” and “rB” for
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tetrahedral A-sites and octahedral B-sites are increased with increased Dy3+ contents. The values
of “rA” and “rB” are calculated following equations.

(10)

(11)

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The distance between magnetic ions (Ion jump lengths) for tetrahedral A-site (LA) and octahedral
B-site (LB) was calculated by following equations.

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LA=a√3/4 (12)
LB=a√2/4 (13)
The calculated values of LA and LB are given in Table 2. The table shows that as lattice constant

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increased with increase in Dy3+ content, the ion jump lengths was also increased . The trend of
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LA and LB with increased Dy3+ contents is shown in Figure 2. The Figure showed clearly that
direct effect of lattice constant on the values of LA and LB as value of lattice constant is directly
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effect on hooping lengths. The cation distribution of ions is very important for understanding the
electrical and magnetic properties of spinel ferrites. Various factors such as cationic radii, field
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effect, electronic distribution and temperature affect the cations distribution. Intensities ratios are
important to calculate the cations distribution. According to Ohnishi and Teranishiin, the planes
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[220] and [422] are most sensitive for cations present on A-site and [400] plane represents the
cations of both sites. To find out the mechanism of Dy 3+ substitution in Mn-ferrites, various
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assumptions were made. According to first assumption, the Dy 3+ ions might have replaced the
Fe3+ ions on B-sites. Secondly, the Dy 3+ ions might have replaced the Fe3+ ion on A-sites and
pushed the Fe3+ ions to B-sites that may increased the magnetic behavior. The third assumption is
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that the Dy 3+ ions may be located in both A and B-sites. For this purpose, calculations of ionic
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radii of A and B sites were made (Table 3). The oxygen parameter or anion parameter (u) was
calculated from XRD data. The oxygen parameter values depend on various factors such as
chemical composition, synthesis route and conditions. The calculated value of ‘u’ obtained
higher than ideal value (0.384>0.375 Å) and found increased with increase in Dy 3+ ions. The
increased value showed the movement of O2- ions away from the cations in tetrahedral site along
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the (111) direction that decreased the dA-A interaction and increased in dB-B interaction. Various
parameters are calculated by following equations [26].
(14)

(15)

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(16)

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(17)

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(18)

All these parameters values are given in Table 3. The site radii (rA & rB) increased with increased

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Dy -contents. Similar trend has been observed for other parameters like dA-A, dB-B etc.

3.5 FTIR Spectral Analysis

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Two main broad bands of Metal-Oxygen (M-O) are the characteristics of spinel ferrites. The
“v1” (high frequency band) corresponds to stretching vibration of tetrahedral A-sites lies in the
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range of 600-500 cm-1, while the “v2” (low frequency band) corresponds to octahedral B-sites
lies in the range of 500-400 cm-1. Lower bond length and large force constant values are
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associated with metal-oxygen bonds of A-site (tetrahedral) which directs the higher stretching
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frequency value as compared to stretching frequency of B-site (octahedral) metal-oxygen bond

[27]. FTIR spectra of all compositions of DyxMnFe2-xO4 nanoparticles are depicted in Figure 3.
These spectra were recorded in the wavenumber range 400-1000 cm-1. It has been observed from
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the spectra that vibrational frequencies (v1 and v2) showed a gradual shift to the lesser frequencies
side for Dy3+ substituted samples. This shifting in bands can be discussed as follows. By
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incorporation of Dy3+ cations at octahedral B- sites will shift the Mn2+ ions towards the
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tetrahedral A-sites. This will transfer the Fe3+ ions from A-sites to B-sites to unwind the strain.
This increased dwelling of Mn2+ ions at A-sites is responsible for high ionic radii of A-sites.
Similarly, by increasing the content of Gd3+ ions at B-sites is also responsible for high ionic radii
of B-sites. In fact, these migrations results for the increase of ionic radii of A and B sites which
contributes to gradual shift of vibrational frequencies (v1 and v2) to the lesser frequencies [38].
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3.6 SEM

Typical SEM image of DyxMnFe2-xO4 nanoparticles is depicted Figure 5. The main purpose of
the scanning electron microscopic analysis was to investigate the surface morphology of the
prepared spinel DyxMnFe2-xO4 ferrite nanoparticles. The particles size could also be estimated

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from SEM images. The estimated size is 80±20 nm. The obtained SEM image confirmed that the
DyxMnFe2-xO4 ferrite nanoparticles have relatively spherical morphology [26].

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3.7 Dielectric Properties

The permittivity or dielectric nature of the ferrite nanoparticles depends upon electric dipole

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moment aroused due to transfer of charge between divalent metal cations and trivalent metal
cations within the spinel crystal structure [39-40]. The frequency dependent dielectric behavior

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of ferrite nanoparticles provides effective behavioral understanding about the localized electric
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charge carriers and information of the mechanism of dielectric polarization [41-42]. Properties
related to permittivity of ferrite mainly depend upon synthetic route, divalent and trivalent
cations distribution with site occupancy, grain density, porosity, grain size, and sintering of the
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prepared ferrite [43].

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In an AC electric field, ferrite shows complex dielectric behavior i.e, Ɛ = Ɛ - j Ɛ″. Where real
part (Ɛ ) represents energy stored and imaginary part (Ɛ″) depicts energy loss. The real and
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imaginary parts of complex dielectric constant were measured by following equations;

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(19)

C = Capacitance of pellet
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d = Thickness of pellet
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A = Cross-sectional area of pellet

The loss tangent (tan δ) and the energy loss (Ɛ″) are related with each other as;

Ɛ″ = Ɛ tan δ (20)
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High dielectric values of ferrite system depict the stored electrostatic energy. Generically, the
dielectric constant behavior of any sample is because of four types of polarization namely
dipolar, ionic or atomic, electronic and interfacial or space charge polarization. Interfacial and
dipolar polarization are considered to be dominant at low frequency. Atomic or ionic and
electronic polarizations are known to show a dominant behavior at higher frequency [28].

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The lower frequency dispersion of Ɛ’ and Ɛ″ is connected to space charge polarization which is

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well explained by Maxwell-Wagner and koops theory [44]. According to theory, ferrite system
generally consists of highly conducting grain and weak conducting boundaries. Ferrite system

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usually has high resistivity at lower frequency range. This behavior is attributed to the space
charge polarization which is the result of conductivity of different phases present. In low
frequency area, electrons reach the poorly conducting grain boundary and start piling up there

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which produces space charge polarization or interfacial polarization [45-47]. At high frequency,
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the chance of hopping electrons gathering at the weakly conducting grain boundary reduces
which ceases interfacial polarization. That’s why the value of Ɛ and Ɛ″ decrease with the
increase in frequency [48]. The dielectric graphs of Dy-substituted MnFe2O4 nanoparticles are
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shown in Figure 6. All these graphs are discussed in detail in following sections.
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3.7 Tan delta (Tan δ)

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The dielectric loss tangent measures the dissipation of electrical energy when ac field is applied
into the prepared ferrite sample at different ranges of frequencies.
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(21)
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Graph shows that there is a rapid loss in energy at low frequency as compared to high frequency.
At high frequency, it almost becomes frequency independent. This behavior of ferrite having
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high resistivity at low frequency can be explained that more energy is needed for electron
hopping between Fe2+ and Fe3+ ions which results high loss.

It can be noticed from the graph that the increment in the value of tan δ with Dy3+ concentration
can be well explained by the reduction in grain size. At higher frequency (≥ 1 MHz), some sort
of peak behavior is noticed. This type of behavior is observed when electron hopping frequency
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of ferrous and ferric ions is almost same to the ac applied frequency and it is known as Debye-
type relaxation [49]. This is also called as loss peak of material and condition for observing is;

Where, is relaxation time.

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max (22)

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max can be calculated from graph.

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It is widely reported in the literature that the substitution of rare earth ions into the spinel ferrite
matrix strongly influence the resistivity and dielectric constant. Here, in our study Dy3+ content

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obviously influence the dielectric constant. The increase in resistivity and dielectric constant can
be explained due to the fact that, by adding Dy3+ content into the manganese ferrite distorted the
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system and bond length of Fe-Dy-O started to increase at octahedral site B. The increment in
bond length gives rise to increase in polarization. Polarization further gives rise in dielectric
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constant and resistivity of the samples. All this structural distortion, induction of microstrain,
changing of electrical and magnetic properties is due to the fact of incorporation of larger ionic
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radius of Dysprosium ions in ferrite system [22- 50].

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The assimilation of Dy3+ ions at octahedral site B reduces the concentration of Fe3+ ions located
there, generating a variation in polarization. Increasing Dy3+ content at octahedral site B restrict
further electrons hopping between ferrous and ferric ions. This restriction constraints the further
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pile-up or congregation of electrons at grain boundaries. This constraints the growth of space-
charge polarization. Due to impedance of space-charge phenomena, the dielectric constant gets
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increased. The anomalous trend in rise in dielectric constant with the substitution of rare earth
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dysprosium ions in spinel ferrite has been also reported earlier [50].

The variation in dielectric constant can be explained in two ways: dy3+ ions substitution in
MnFe2O4 vary the dielectric constant by turning the cations into more diversified form, which
may originate the multidipoles with the (O2-) anions to enhance the dipole polarization. Dy3+ ion
substitution may also enhance the charge (e-) hopping which favor the Fe2+ conversion into Fe3+
ion that result in decrease in conductance losses. Furthermore, the ionic radius of Dy3+ ion
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(0.104nm) is markedly larger than that of the Fe3+ (0.067nm). Therefore, lattice parameter ‘a’ of
the substituted MnFe2O4 increases which causes distortion in the lattice. Physical activity gets
increased which is responsible for increase in dielectric losses (Ɛ″) [51].

4. Conclusion

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We have successfully synthesized single phase Dy3+ substituted Mn-ferrite nanoparticles with
cubic structure via low cost, low sintering temperature micro-emulsion method. Pure spinel

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structure was confirmed with XRD technique and various parameters calculated from XRD data.
As Dy3+ ion contents increased, the lattice constant ‘a’ was also increased. X-ray density

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increased with substitution of rare earth metal cations. Ion jump lengths increased with increase
in lattice constant. Oxygen parameter ‘u’ found to increase due to substitution of Dy3+ ions.
Distribution of cations between A-sites and B-sites was calculated. FTIR spectra confirmed the

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single phase cubic spinel identifying the two absorption bands. High frequency bands “ν1” was
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observed between 600-500 cm-1 due to the intrinsic vibrations of tetrahedral complexes and low
frequency band “ν2” was observed between 500-400 cm-1 due to octahedral complexes.
Dielectric parameters were explained with the support of space charge polarization mechanism.
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These parameters were decreased with increase in frequency. The low loss values at higher
frequencies suggested the various potential applications of these ferrite particles in high
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frequency microwave devices fabrication.

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Acknowledgement: Dr. Imran Shakir and Dr. Philips Agboola would like to extend their sincere
appreciation to the Deanship of Scientific Research (DSR) at King Saud University for its
funding of this research through the Research Group no. RG-1438-068. Authors are thankful to
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the Islamia University of Bahawalpur and Higher Education Commission (HEC) of Pakistan.
References
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[1] A. Manzoor, M.A. Khan, M. Shahid, M.F. Warsi, Investigation of structural, dielectric and
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List of Tables

Table 1: Various XRD parameters of Dy3+ substituted MnFe2O4 nanoparticles.

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Table 2: The values of hoping lengths LA and LB for Dy3+ substituted MnFe2O4 nanoparticles.

Table 3: Site radii and Bond length calculation of Dy3+ substituted MnFe2O4 from XRD data.

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Table 4: FTIR wave number (ν1, ν2) of Dy3+ substituted Manganese Ferrites.

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Table 5: EDX data of Manganese Ferrites (Dy-0).

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Table 1: Various cell and other physical parameters of Dy3+ substituted MnFe2O4 nanoparticles.

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Crystal X-ray Bulk
Cell
sample lattice Crystallite density/ density
Volume/Vcell 3
%P

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No. parameter size (nm) dx (g/cm ) (db)
(Å3)
a (Å) (g/cm3)

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Dy-0 8.4734 608.38 13.40 5.03 3.23 36

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Dy-1 8.4839 610.64 11.6 5.04 2.72 46
Dy-2 8.4774 609.24 13.8 5.07 3.02 41
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Dy-3 8.4811 610.04 16.17 5.11 2.91 43
Dy-4 8.4746 608.64 12.15 5.22 2.96 43
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Dy-5 8.4978 613.65 11.5 5.36 3.01 44

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Table 2: The values of hoping lengths LA and LB for Dy3+ substituted MnFe2O4 nanoparticles.
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sample LA LB
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Dy-0 3.6691 2.9958

Dy-1 3.6736 2.9995
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Dy-2 3.6708 2.9972

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Dy-3 3.6724 2.9985

Dy-4 3.6696 2.9962
Dy-5 3.6797 3.0044
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Table 3: Various physical parameters determined from XRD data of Dy3+ substituted MnFe2O4.

sample Site radii Bond length

rA(A°) rB(A°) dA-A(A°) dB-B(A°) dA-B(A°) dA-O (A°) dB-O (A°)

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Dy-0 0.6151 0.6929 3.6690 2.9958 3.5129 1.9651 2.0532
Dy-1 0.6175 0.6955 3.6735 2.9995 3.5172 1.9675 2.0557

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Dy-2 0.6160 0.6939 3.6707 2.9972 3.5145 1.9660 2.0542
Dy-3 0.6169 0.6948 3.6723 2.9985 3.5161 1.9669 2.0551

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Dy-4 0.6154 0.6932 3.6695 2.9962 3.5134 1.9654 2.0535
Dy-5 0.6208 0.6988 3.6795 3.0044 3.5230 1.9708 2.0591

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Table 4: ν1 and ν2 band positions in FTIR spectra of Dy3+ substituted manganese ferrites.
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Sample ν1 (cm-1) ν2 (cm-1)

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Dy-0 534 442

Dy-1 538 431
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Dy-2 550 451

Dy-3 546 451
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Dy-4 529 448

Dy-5 542 467
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Table 5: EDX data of Manganese Ferrites (Dy-0).

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Element Weight % Atomic %

CK 9.95 18.02

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OK 48.41 65.82

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Mn K 11.79 4.67

Fe K 27.54 10.73

Zn K
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Total 100
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List of Figures
Figure 1: (a) XRD pattern of Dy3+ substituted MnFe2O4 (b) Peak shifting (c) Graph between

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concentration (x) with lattice constant (a) and crystallite size (nm).

Figure 2: The values of hoping lengths LA and LB for Dy3+ substituted MnFe2O4 nanoparticles.

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Figure 3: Proposed mechanism of one pot (single) micro-emulsion for synthesis of

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nanoparticles.

Figure 4: FTIR spectra of MnYxFe2-xO4 nanoparticles.

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Figure 5: SEM image of manganese ferrites nanoparticles .
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Figure 6: (a) Real part of dielectric permittivity (b) Imaginary part of dielectric permittivity
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(c) Tan loss Vs frequency of MnYxFe2-xO4 nanoparticles.

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Figure 1: (a) XRD pattern of Dy3+ substituted MnFe2O4 (b) Peak shifting (c) Graph between
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Concentration (x) with Lattice constant (a) and Crystallite size (nm).
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Figure 2: The values of hoping lengths LA and LB for Dy3+ substituted MnFe2O4 nanoparticles.
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Figure 3: Proposed mechanism of one pot (single) microemulsion for synthesis of ferrite
nanoparticles.
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Figure 4: FTIR spectra of YxMnFe2-xO4 nanoparticles.

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Figure 5: SEM image of Manganese Ferrites nanoparticles.

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Figure 6: (a) Real part of dielectric permittivity (b) Imaginary part of dielectric permittivity
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(c) Tan loss Vs frequency of MnDyxFe2-xO4 nanoparticles.

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