<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">MSA</journal-id><journal-title-group><journal-title>Materials Sciences and Applications</journal-title></journal-title-group><issn pub-type="epub">2153-117X</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/msa.2021.123008</article-id><article-id pub-id-type="publisher-id">MSA-108005</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject></subj-group></article-categories><title-group><article-title>
 
 
  Impact of Cr Substitution on Structural, Magnetic, Electric and Impedance Study of Mn-Ni-Zn Ferrites
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Shanzida</surname><given-names>Haque</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Sajal</surname><given-names>Chandra Mazumdar</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref><xref ref-type="corresp" rid="cor1"><sup>*</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mohammed</surname><given-names>Nazrul Islam Khan</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Mithun</surname><given-names>Kumar Das</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib></contrib-group><aff id="aff2"><addr-line>Material Science Division, Atomic Energy Centre, Dhaka, Bangladesh</addr-line></aff><aff id="aff1"><addr-line>Department of Physics, Comilla University, Cumilla, Bangladesh</addr-line></aff><pub-date pub-type="epub"><day>25</day><month>03</month><year>2021</year></pub-date><volume>12</volume><issue>03</issue><fpage>121</fpage><lpage>138</lpage><history><date date-type="received"><day>9,</day>	<month>February</month>	<year>2021</year></date><date date-type="rev-recd"><day>23,</day>	<month>March</month>	<year>2021</year>	</date><date date-type="accepted"><day>26,</day>	<month>March</month>	<year>2021</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
  A series of Cr
  <sup>3+</sup>-substituted Mn-Ni–Zn ferrites; Mn
  <sub>0.5</sub>Ni
  <sub>0.1</sub>Zn
  <sub>0.4</sub>Fe
  <sub>2-x</sub>Cr
  <sub>x</sub>O
  <sub>4</sub> (
  <em>x</em> = 0.0 - 0.4 in a step of 0.1) were prepared by traditional solid-state reaction route. The structural, magnetic, dielectric properties and impedance spectroscopy of these compositions were studied. Phase identification and lattice constant (a
  <sub>0</sub>) determination were carried out by X-ray diffraction (XRD). The XRD patterns established the fabrication of a single-phase spinel structure. The FESEM micrographs exposed that the average grain size (
  <inline-formula><inline-graphic xlink:href="dit_da92e8c9-165d-4d71-aaf5-717db2aa65e1.png" xlink:type="simple"/></inline-formula>) increased slightly with chromium (Cr) substitution and then decreased for a higher concentration of chromium in the composition. The real part of initial permeability (
  <inline-formula><inline-graphic xlink:href="dit_1d356971-e483-44dc-875c-698f938e7d9f.png" xlink:type="simple"/></inline-formula>) diminished owing to the enhanced porosity of the compositions with the increase of Cr
  <sup>3+</sup> content in the composition. The highest relative quality factor (RQF) was attained for the samples with x = 0.1. The magnetic hysteresis was investigated to know the effect of Cr
  <sup>3+</sup> substitution in the composition of the magnetic properties. The decrease of saturation magnetization (
  <em>M<sub>s</sub></em>) with an enhancement in Cr
  <sup>3+</sup> might be triggered by switching of Fe
  <sup>3+</sup> ions from octahedral to tetrahedral site. The samples with x = 0.1 exhibited the highest anisotropy constant (
  <em>K</em>). Curie temperatures of the investigated samples were significantly modified to lower temperatures with the Cr
  <sup>3+</sup> content. The frequency characteristics of dielectric properties and impedance spectroscopy had been investigated. The highest dielectric constant (
  <em>&amp;epsilon;'</em>) and resistivity were observed for x = 0.1 and x = 0.2 samples. The complex impedance spectra analysis reveals in-depth information about the conduction mechanism, microstructure, and orientation of the grains in the samples.
 
</p></abstract><kwd-group><kwd>X-Ray Diffraction</kwd><kwd> Permeability</kwd><kwd> Dielectric Property</kwd><kwd> Curie Temperature</kwd><kwd> Impedance Spectroscopy</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>During the last few decades, ferrites are materials of great interest owing to their notable magnetoelectric properties. According to the structure, they have tetrahedral A-site and octahedral B-sites in the AB<sub>2</sub>O<sub>4</sub> crystal lattice. These materials exhibit diverse magnetic and electrical properties subject to their cation distribution of the chemical compositions. Numerous cations could be located on the A-site and B-sites to modify their magnetic properties [<xref ref-type="bibr" rid="scirp.108005-ref1">1</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref2">2</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref4">4</xref>]. Sivakumar et al. [<xref ref-type="bibr" rid="scirp.108005-ref1">1</xref>] studied the effect of milling, grain size, frequency, and temperature on the dielectric properties of nanocrystalline Ni-Zn ferrites. They found an unusual rise in dielectric loss with milling resulting from increased electrical conductivity due to oxygen vacancies introduced upon milling. On the other hand, the relaxation frequency was observed to decrease with milling due to increased interaction between charge carriers. Hossain et al. [<xref ref-type="bibr" rid="scirp.108005-ref2">2</xref>] observed that with the increase in Zn content in Ni-ferrite the Curie temperature (T<sub>c</sub>), resistivity, and the activation energy dropped off whereas the magnetization, initial permeability, and the relative quality factor (Q) increased. A Hopkinson peak was obtained near T<sub>c</sub> in the real part of the initial permeability vs. temperature curves. Chukalkin et al. [<xref ref-type="bibr" rid="scirp.108005-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref6">6</xref>] and Mahmud et al. [<xref ref-type="bibr" rid="scirp.108005-ref6">6</xref>] observed the effect of Zn substitution on the magnetic properties Ni-Zn ferrites. Local angular structures of spin were evident for x = 0.45 with effective sizes of 1 - 10 nm [<xref ref-type="bibr" rid="scirp.108005-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref6">6</xref>].Rezlescu et al. studied the effect of divalent ions [<xref ref-type="bibr" rid="scirp.108005-ref7">7</xref>] and rare earth ions [<xref ref-type="bibr" rid="scirp.108005-ref8">8</xref>] on the structural, magnetic and electric properties of Ni-Zn ferrites.</p><p>From the functional viewpoint, Mn-Zn along with Ni-Zn ferrites epitomizes the most significant types. These are utilized in various ferrite devices for instance converters, inductor cores, electromagnetic wave absorbers, recording heads, etc. Mn-Zn ferrites own high μ ′ i and magnetization but these are not appropriate for magnetic uses at higher frequencies owing to their high electrical conductivity and excessive power losses. In contrast, Ni-Zn ferrites have giant resistivity, small-dielectric loss (tanδ<sub>E</sub>), and high Curie temperature (T<sub>C</sub>), but they have somewhat minimal μ ′ i at higher frequencies. Several authors considered the mixture of these two ferrites to obtain encouraging magnetic characteristics with moderate losses particularly in the excessive frequency range [<xref ref-type="bibr" rid="scirp.108005-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref10">10</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref11">11</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref12">12</xref>]. In earlier studies, the magnetic and electrical effects of this sort of mixture were evaluated [<xref ref-type="bibr" rid="scirp.108005-ref12">12</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref13">13</xref>]. The composition Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2</sub>O<sub>4</sub> was found to possess the optimum magnetic characteristics for auspicious functions [<xref ref-type="bibr" rid="scirp.108005-ref12">12</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref15">15</xref>]. Preferential occupation of Cr<sup>3+</sup> ions by octahedral sites in Ni-Zn ferrites replaces Fe<sup>3+</sup> ions limiting Fe<sup>2+</sup>-Fe<sup>3+</sup> hoping conduction and increases resistivity. Accordingly, in the present work, we are interested to deal with the enhancement of the electrical properties of the optimum composition Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2</sub>O<sub>4</sub> by substituting Cr<sup>3+</sup> ions in octahedral B-site.</p></sec><sec id="s2"><title>2. Materials and Methods</title><p>The Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> (where x = 0.0 - 0.4) samples were fabricated by standard solid-state reaction technique. High purity (99.9%) crushes of MnCO<sub>3</sub>, NiO, ZnO, Cr<sub>2</sub>O<sub>3,</sub> and Fe<sub>2</sub>O<sub>3</sub> were utilized as untreated substances for the synthesis of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> compositions. The constituents in requisite stoichiometric amounts were mixed mechanically by hand milling in acetone media using a ceramic mortar for 6 hours and calcined in ambient air at 700˚C for 3 hours. Afterward, the calcined powders were shaped into pellets and rings by a hydraulic press. After that, the samples were sintered at 1100˚C, 1150˚C and 1200˚C for 3 hours. The temperature variation for sintering was 5˚C/min during heating and 10˚C/min during cooling. The compositions sintered at 1150˚C were reserved for characterization based on optimum density. Some of these samples were polished for complex initial permeability and electrical characterization.</p><p>The XRD of the samples was performed using PHILIPS PW 3040 X’pert PRO X-ray diffractometer. The Nelson-Riley process was utilized for determining the precise a<sub>0</sub>of the samples. The Nelson-Riley (N-R) function F(θ) is specified by</p><p>F ( θ ) = 1 2 ( cos 2 θ sin θ + cos 2 θ θ ) (1)</p><p>where θ demonstrates the Bragg angle. The values of a<sub>0</sub>for all the peaks of a sample were plotted as a function of F(θ). After that utilizing the least square fitting method precise lattice constants were found out. The point where the least square fitting straight line meets the y-axis (i.e. at F(θ) = 0) is the real a<sub>0</sub>of the sample.</p><p>Bulk density (ρ<sub>B</sub>) of all the samples was measured by the formulae [<xref ref-type="bibr" rid="scirp.108005-ref16">16</xref>]:</p><p>ρ B = m π r 2 t (2)</p><p>where m, r, and t represent the mass, radius, and thickness of the pellet or ring, individually. The X-ray density (ρ<sub>x</sub>) was computed applying the following expression:</p><p>ρ x = n M N A V (3)</p><p>where n,M,N<sub>A</sub>, and V reflect the number of atoms in a unit cell, the molar mass, Avogadro’s number, and unit cell volume, separately. The porosity (P) was determined from the expression</p><p>P ( % ) = ρ x − ρ B ρ x &#215; 100 % (4)</p><p>The electromagnetic properties were characterized at ambient temperature as a function of frequency using WAYNE KERR 6500B Impedance Analyzer. The μ ′ i was calculated with the following relations [<xref ref-type="bibr" rid="scirp.108005-ref17">17</xref>]:</p><p>μ ′ i = L s L 0 (5)</p><p>and L 0 = μ 0 N 2 S π d &#175; (6)</p><p>where, L<sub>s</sub> is the self-inductance of the sample core and L<sub>0</sub> is the winding coil inductance in absence of sample core, N is the number of windings of the coil (N = 5), S is the cross-sectional area of the ring-shaped sample, S = d &#215; h , where, d = d 2 − d 1 2 and d &#175; = d 1 + d 2 2 is the mean diameter of the ring-shaped sample. The RQF was settled from the ratio, μ ′ i tan δ M . The T<sub>C</sub> of the compositions was computed from the temperature-controlled μ ′ i .</p><p>For dielectric measurements, disk-shaped samples have been painted with silver paste on both sides for better electrical contact. The ɛ' was estimated using the given formula [<xref ref-type="bibr" rid="scirp.108005-ref3">3</xref>]:</p><p>ε ′ = C C 0 (7)</p><p>and ε ″ = ε ′ tan δ E (8)</p><p>where C is the capacitance of the dielectric materials and C 0 = ε 0 A t is resulting geometrically. Here C<sub>0</sub> is the capacitance of the capacitor in the absence of dielectric specimens, ε<sub>0</sub> is the permittivity of free space (ε<sub>0</sub> = 8.85 &#215; 10<sup>−12</sup> Fm<sup>−1</sup>),t is the thickness and A ( = π r 2 ) is the cross-sectional area of the sample painted with silver paste.</p><p>Dielectric relaxation and conduction processes were accomplished in the complex modulus (M<sup>*</sup>) spectra. The real (M') and imaginary (M'') segments of electric modulus were picked up from the dielectric data from the relations:</p><p>M ′ = ε ′ ε ′ 2 + ε ″ 2 (9)</p><p>and M ″ = ε ″ ε ′ 2 + ε ″ 2 (10)</p></sec><sec id="s3"><title>3. Results and Discussion</title><sec id="s3_1"><title>3.1. X-Ray Diffraction, Lattice Constant, Density, and Porosity</title><p>XRD patterns for the samples Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> (x = 0.0, 0.1, 0.2, 0.3, 0.4) sintered at 1150˚C for 3 hours are represented in <xref ref-type="fig" rid="fig1">Figure 1</xref>. The peaks in the XRD patterns disclose the single-phase spinel structure. The position of the XRD peaks is in good concurrence with other reports [<xref ref-type="bibr" rid="scirp.108005-ref17">17</xref>]. The a<sub>0</sub>, density, and P of the samples are presented in <xref ref-type="table" rid="table1">Table 1</xref>. To find the precise value of a<sub>0</sub>, all the values of a<sub>0</sub> are plotted against the N-R function. The exact value of a<sub>0</sub>of the sample is that point where the least square fitting straight line cuts the Y-axis. By plotting</p><table-wrap id="table1" ><label><xref ref-type="table" rid="table1">Table 1</xref></label><caption><title> The a<sub>0</sub>, ρ<sub>B</sub>, ρ<sub>x</sub>,P, and D &#175; of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> ferrites</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >Content (x)</th><th align="center" valign="middle" >a<sub>0</sub> (&#197;)</th><th align="center" valign="middle" >ρ<sub>B</sub> (g/cm<sup>3</sup>)</th><th align="center" valign="middle" >ρ<sub>x</sub> (g/cm<sup>3</sup>)</th><th align="center" valign="middle" >P (%)</th><th align="center" valign="middle" >D &#175; (&#181;m)</th></tr></thead><tr><td align="center" valign="middle" >0.0</td><td align="center" valign="middle" >8.51</td><td align="center" valign="middle" >4.70</td><td align="center" valign="middle" >5.21</td><td align="center" valign="middle" >9.79</td><td align="center" valign="middle" >0.0861</td></tr><tr><td align="center" valign="middle" >0.1</td><td align="center" valign="middle" >8.50</td><td align="center" valign="middle" >4.71</td><td align="center" valign="middle" >5.26</td><td align="center" valign="middle" >10.46</td><td align="center" valign="middle" >0.1280</td></tr><tr><td align="center" valign="middle" >0.2</td><td align="center" valign="middle" >8.52</td><td align="center" valign="middle" >4.63</td><td align="center" valign="middle" >5.29</td><td align="center" valign="middle" >12.48</td><td align="center" valign="middle" >0.1312</td></tr><tr><td align="center" valign="middle" >0.3</td><td align="center" valign="middle" >8.46</td><td align="center" valign="middle" >4.59</td><td align="center" valign="middle" >5.23</td><td align="center" valign="middle" >12.24</td><td align="center" valign="middle" >0.0846</td></tr><tr><td align="center" valign="middle" >0.4</td><td align="center" valign="middle" >8.52</td><td align="center" valign="middle" >4.49</td><td align="center" valign="middle" >5.22</td><td align="center" valign="middle" >13.98</td><td align="center" valign="middle" >0.0876</td></tr></tbody></table></table-wrap><p>the a<sub>0</sub>against Cr content in <xref ref-type="fig" rid="fig2">Figure 2</xref>, it appears that the value of the a<sub>0</sub>drops up to x = 0.3 with increasing the value of Cr content showing inconsistency for x = 0.2 and then rises with Cr content. This drop of the a<sub>0</sub>with increasing Cr content establishes the fact that the a<sub>0</sub>is proportional to the rise of the ionic radius as the ionic radius of Cr<sup>3+</sup> (0.64 &#197;) is less than that of Fe<sup>3+</sup> (0.67 &#197;) [<xref ref-type="bibr" rid="scirp.108005-ref18">18</xref>]. After x = 0.3, the a<sub>0</sub>rises with increasing Cr content. The rise in the a<sub>0</sub> for a higher concentration of Cr was also observed by Li et al. [<xref ref-type="bibr" rid="scirp.108005-ref19">19</xref>] The rise in the a<sub>0</sub> for a higher concentration of Cr may be due to the fact that instead of trivalent the divalent Cr ion substitutes Fe<sup>2+</sup> in the A-site which results in the increase of lattice constant as the lattice constant of Cr<sup>2+</sup> is larger than that of Fe<sup>2+</sup> [<xref ref-type="bibr" rid="scirp.108005-ref19">19</xref>]. Another possible reason is: the oxides of Cr reside at the grain boundary (as seen from the micrographs in section 3.2) thereby obstructing the grain growth and exerts a stress on the unit cell. To compensate for the stress exerted by the grain boundary, the a<sub>0</sub>rises for higher Cr<sup>3+</sup> concentration. The inconsistency from the declining trend for x = 0.2 may be caused by the inhomogeneous diffusion of Cr<sup>3+</sup> in the lattice.</p><p>The alteration of ρ<sub>B</sub> and X-ray density (ρ<sub>x</sub>) of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> is understood from <xref ref-type="fig" rid="fig3">Figure 3</xref>. It is perceived that the ρ<sub>x</sub>rises with Cr content linearly up to x = 0.2 and this is because the reduction in the volume of the unit cell increases the density of the sample. Unit cell volume is calculated using the formula V = a 0 3 . Unit cell volume is reduced with rising Cr content until x = 0.2 as it depends on the a<sub>0</sub>which is also reduced with reducing Cr content. From the graph, it is perceived that the ρ<sub>x</sub>is higher than the ρ<sub>B</sub>one which means that when the samples are sintered, they might contain cracks and pores on the microscopic scale and vacancies in the lattice on the atomic scale [<xref ref-type="bibr" rid="scirp.108005-ref20">20</xref>]. It is observed from <xref ref-type="table" rid="table1">Table 1</xref> that the variation of P of the sample behaves exactly in the opposite manner to that of the ρ<sub>B</sub>. The ρ<sub>B</sub>is diminished with increasing Cr<sup>3+</sup> because the atomic mass of Cr<sup>3+</sup> is less than that of Fe<sup>3+</sup>. Moreover, the influence of the residual stress decreases the D &#175; and increases P.</p></sec><sec id="s3_2"><title>3.2. Microstructure</title><p>For the morphological study, a microstructural image of Mn-Ni-Zn-Cr ferrite samples sintered at 1150˚C was taken using FESEM (Model no. JEOL JSM 7600F) so that an insight of grain structure can be understood. The linear intercept technique was employed to determine the mean grain diameter of the samples.</p><p>It is evident from <xref ref-type="fig" rid="fig4">Figure 4</xref> that the D &#175; is increased with Cr content until x = 0.2 because the doped Cr<sub>2</sub>O<sub>3</sub> becomes liquid phase in optimized oxygen potential and that liquid phase stimulates the grain growth. The D &#175; decreases for x = 0.3 and x = 0.4 which may be due to the fact that higher compounds can act as obstacles for visco-plastic deformation and Cr<sup>3+</sup> resides at the grain boundary and hinders the grain growth. Grain growth and grain boundary mobility are very closely related to each other. Once the homogeneous driving force of grain</p><p>boundary is attained, the sintered body achieves a unified grain size distribution. The compositional variation of the samples affects the grain size distribution. The grain size reflects the presence of a lesser grain boundary area. The pores are left behind the fast-moving grain boundaries and are confined within the grains only when the grain expansion rate is very high.</p></sec><sec id="s3_3"><title>3.3. Magnetic Characterization</title><sec id="s3_3_1"><title>3.3.1. Complex Initial Permeability</title><p>The μ ′ i provides a precise description of the stored energy by expressing magnetic induction with the magnetic field. The μ ′ i has been measured against frequency in the range 10 kHz - 120 MHz at ambient temperature for all the samples of the series Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub>. From <xref ref-type="fig" rid="fig5">Figure 5</xref>, it is noted that with the rise in frequency, the μ ′ i remains stable up to a particular frequency, and after that μ ′ i falls rapidly. Generally, the ferri-magnetic order of ferrite develops from anti-parallel and unequal spin moments in the neighboring magnetic sub-lattices which is determined by the distribution of the transition metal ions [<xref ref-type="bibr" rid="scirp.108005-ref21">21</xref>]. A substantial amount of Fe<sup>3+</sup> ions reside in the octahedral sub-lattice in Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub>. So, the Cr<sup>3+</sup> ion leads the Fe<sup>3+</sup> ions to enter into the tetrahedral sub-lattice. Thus the doped sample will show the antiferromagnetic character and the remarkable reduction of μ ′ i with the rise of Cr<sup>3+</sup> results due to this antiferromagnetic behavior of the samples as in <xref ref-type="fig" rid="fig5">Figure 5</xref>.</p><p>The frequency dependence of the magnetic loss tangent (tanδ<sub>M</sub>) of the composition Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> sintered at 1150˚C at ambient temperature over the range 10 kHz - 120 MHz is illustrated in <xref ref-type="fig" rid="fig6">Figure 6</xref>. The value of tanδ<sub>M</sub> decreases with frequency arriving at the lowest value and after that becomes nearly constant. The grounds behind reducing tanδ<sub>M</sub> with increasing frequency is that, beyond the definite frequency of the electric field, the domain wall motion cannot go along with the external electric field. It is perceived that the tanδ<sub>M</sub> reduces significantly with the Cr content at a very high frequency. The low value of the tanδ<sub>M</sub>is the main requirement for the high-frequency magnetic application [<xref ref-type="bibr" rid="scirp.108005-ref16">16</xref>].</p><p>The frequency dependence of the RQF of the compositions of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4 </sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> sintered at 1150˚C at ambient temperature over the range 10 kHz - 120 MHz is illustrated in <xref ref-type="fig" rid="fig7">Figure 7</xref>. It is perceived that RQF enhances with frequency and after a certain frequency RQF slightly reduces with the rise of frequency.</p><p>RQF has the highest magnitude at a certain frequency where the tanδ<sub>M</sub> has the lowest magnitude [<xref ref-type="bibr" rid="scirp.108005-ref22">22</xref>]. RFQ’s improvement can be attributed to the 10% of Cr addition and this addition is expected to decrease the M<sub>s</sub>. The RQF is often used as a measure of performance for inductors used in filtering action.</p></sec><sec id="s3_3_2"><title>3.3.2. Temperature-Dependent Complex Initial Permeability</title><p>Curie temperature (T<sub>c</sub>) measurement is one of the most significant measurements for magnetic materials. The T<sub>c</sub>gives substantial information on the magnetic status of a substance for the strength of exchange interaction. The temperature-dependent μ ′ i for Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> is depicted in <xref ref-type="fig" rid="fig8">Figure 8</xref>. The μ ′ i is measured at a fixed frequency of 100 kHz. The μ ′ i drops rapidly at the temperature when the magnetism of the samples shifts from ferromagnetic to paramagnetic (at Curie point). The sharp fall of μ ′ i with temperature represents the degree of homogeneity of the samples [<xref ref-type="bibr" rid="scirp.108005-ref23">23</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref24">24</xref>]. In the present case instead of sharp fall μ ′ i drops rapidly owing to the presence of crack and pores within the samples. It is revealed from <xref ref-type="fig" rid="fig8">Figure 8</xref> that when Cr<sup>3+</sup> is doped in Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2</sub>O<sub>4</sub>, T<sub>c</sub> decreases. The decline in T<sub>C</sub> is mainly attributable to the weakening of the A-B interaction, which is confirmed from that the ionic radius of Cr<sup>3+</sup> (0.64 &#197;) is less than Fe<sup>3+</sup> (0.67 &#197;). Due to the replacement of Fe<sup>3+</sup> by Cr<sup>3+</sup>, the longest distance between moments causes a decrease in A-B interaction in</p><p>the Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2</sub>O<sub>4</sub> relative to all other samples, and consequently, T<sub>c</sub>decreases [<xref ref-type="bibr" rid="scirp.108005-ref4">4</xref>].</p></sec><sec id="s3_3_3"><title>3.3.3 Magnetic Hysteresis Loop</title><p>Measurement of magnetic hysteresis loop and magnetization for all the samples of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> were carried out by using Vibrating Sample Magnetometer. Observation of <xref ref-type="fig" rid="fig9">Figure 9</xref> showed that M<sub>s</sub>reduces with the rise of Cr<sup>3+</sup> concentration. This happens since the substituted Cr<sup>3+</sup> ion has a site preference to occupy B-site which makes the iron enter into the A-site from B-site. As a consequence, the exchange interaction between A and B sites turns weaker resulting in intensifying the B-B interaction and weakening the A-B interaction, which in turn reduces the M<sub>s</sub>of the samples. Besides, Cr has less magnetic moment than Fe, which may be another reason for the reduction of magnetization with Cr content. Similar results were reported in other reports [<xref ref-type="bibr" rid="scirp.108005-ref25">25</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref26">26</xref>]. The samples having x = 0.1 confirmed improved ferromagnetic property as shown in <xref ref-type="table" rid="table2">Table 2</xref>.</p></sec></sec><sec id="s3_4"><title>3.4. Electrical Characterization</title><sec id="s3_4_1"><title>3.4.1. Dielectric Property</title><p>The variation of frequency-dependent ε' of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> at ambient temperature is illustrated in <xref ref-type="fig" rid="fig1">Figure 1</xref>0. It can be realized that the ε' drops rapidly with a rise in frequency thereby showing dispersion in the low-frequency range</p><table-wrap id="table2" ><label><xref ref-type="table" rid="table2">Table 2</xref></label><caption><title> The M<sub>s</sub>, coercivity (H<sub>c</sub>), K, remanent magnetization (M<sub>r</sub>) of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> ferrites</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >Content, (x)</th><th align="center" valign="middle" >M<sub>s</sub> (emu/g)</th><th align="center" valign="middle" >H<sub>c</sub> (T)</th><th align="center" valign="middle" >K</th><th align="center" valign="middle" >M<sub>r</sub> (emu/g)</th></tr></thead><tr><td align="center" valign="middle" >0.0</td><td align="center" valign="middle" >61.58</td><td align="center" valign="middle" >2.241</td><td align="center" valign="middle" >69.00</td><td align="center" valign="middle" >0.169</td></tr><tr><td align="center" valign="middle" >0.1</td><td align="center" valign="middle" >46.31</td><td align="center" valign="middle" >4.367</td><td align="center" valign="middle" >101.118</td><td align="center" valign="middle" >0.213</td></tr><tr><td align="center" valign="middle" >0.2</td><td align="center" valign="middle" >41.22</td><td align="center" valign="middle" >1.928</td><td align="center" valign="middle" >39.73</td><td align="center" valign="middle" >0.282</td></tr><tr><td align="center" valign="middle" >0.3</td><td align="center" valign="middle" >36.09</td><td align="center" valign="middle" >2.206</td><td align="center" valign="middle" >39.80</td><td align="center" valign="middle" >0.079</td></tr><tr><td align="center" valign="middle" >0.4</td><td align="center" valign="middle" >8.31</td><td align="center" valign="middle" >4.697</td><td align="center" valign="middle" >19.52</td><td align="center" valign="middle" >0.071</td></tr></tbody></table></table-wrap><p>and become constant at the high-frequency range. The observed dispersion at lower frequencies can be interpreted applying Maxwell-Wagner interfacial polarization which plays a crucial role in such a heterogeneous system [<xref ref-type="bibr" rid="scirp.108005-ref27">27</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref28">28</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref29">29</xref>]. The high values of ε' observed at low-frequency range are because of the presence of the heterogeneity in the composition. Heterogeneities in the samples initiate space charge polarization and contribute towards the high values of ε'. As Cr content rises, the amount of space charge also rises. The reduction of Fe<sup>3+</sup> concentration causes the transport of some Mn<sup>2+</sup> in the octahedral site which causes an enhancement of hopping charge carriers and consequently provides a high value of ε'. <xref ref-type="fig" rid="fig1">Figure 1</xref>1 displays the variation of ε' with Cr content at a frequency of 100 kHz. The highest ε' is obtained for the sample with x = 0.4. The grain boundary impedance decreases due to the presence of the second phase in between grains for high Cr content which in turn increases ε'.</p><p>The variation of tanδ<sub>E</sub> as a function of the frequency of the composition Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> is shown in <xref ref-type="fig" rid="fig1">Figure 1</xref>2 sintered at 1150˚C. The tanδ<sub>E</sub>unveils the similar nature of ɛ'. This means that at low frequency the tanδ<sub>E</sub>is high and drops with frequency. The tanδ<sub>E</sub>is proportional to the “loss of energy” from the applied field in the ferrite (in fact this energy is wasted as heat) and hence designated as a tanδ<sub>E</sub>. The tanδ<sub>E</sub> arises in materials due to the phase difference between polarization and applied field in the high-frequency region.</p></sec><sec id="s3_4_2"><title>3.4.2. AC Resistivity</title><p>The significant electrical property resistivity is an intrinsic property of magnetic material. The resistivity of Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> sintered at 1150˚C was calculated and plotted against frequency as shown in <xref ref-type="fig" rid="fig1">Figure 1</xref>3. It is observed that AC resistivity also shows significant dispersion as ɛ' at lower frequencies due to the dominant space charge polarization. At low-frequency AC resistivity rises with Cr content up to x = 0.2 and then reduces with a further rise of Cr content because the ɛ' is high for samples with higher Cr concentration i.e., for x = 0.3 and x = 0.4. It is found that ac resistivity reduces with frequency showing significant dispersion and this dispersion is more at low-frequency range which might be due to the variation in the concentration of Fe<sup>3+</sup>/Fe<sup>2+</sup> and other ions in various samples [<xref ref-type="bibr" rid="scirp.108005-ref30">30</xref>].</p></sec></sec><sec id="s3_5"><title>3.5. Complex Impedance Spectra Analysis</title><p>Transport properties are strongly dependent on microstructure in polycrystalline solids, and impedance spectra generally include functionalities that may be</p><p>specifically linked to microstructure. <xref ref-type="fig" rid="fig1">Figure 1</xref>4(a) demonstrates the alteration of resistance (Z') with the frequency of the samples at ambient temperature. The higher value of Z' at lower frequency is due to the dominant space charge polarization [<xref ref-type="bibr" rid="scirp.108005-ref31">31</xref>]. Observation confirms that with the rise in frequency up to a specific limit (~1 kHz), the value of Z' rapidly decreases which means conductivity of the ferrite samples increases [<xref ref-type="bibr" rid="scirp.108005-ref32">32</xref>]. As all types of polarization are present at the lower frequency it gives higher magnitudes of Z'. But at the high-frequency region, the values of Z' decreases as the contribution from different parts of polarization ceases, this is because only electronic polarization can carry over the fast variation of field frequency [<xref ref-type="bibr" rid="scirp.108005-ref33">33</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref34">34</xref>]. The alteration of reactance (Z&quot;) with the frequency is illustrated in <xref ref-type="fig" rid="fig1">Figure 1</xref>4(b). The frequency dependence of Z&quot; [<xref ref-type="fig" rid="fig1">Figure 1</xref>4(b)] behaves similarly as Z' in addition to the appearance of some relaxation peaks due to immobile charges.</p><p>According to the brick-layer model, an equivalent circuit comprising of three parallel RC circuits can explain polycrystalline ceramics [<xref ref-type="bibr" rid="scirp.108005-ref35">35</xref>]. Each RC component of the equivalent circuit produces a semicircle in the Z' vs Z'' plot (Cole-Cole diagram). A single semicircle at a higher frequency in Z' vs Z'' plot specifies grain effect, the second semicircle at a lower frequency specifies the presence of grain boundary effect, and a third semicircular arc or spike is often observed which is due to the electrode effect. <xref ref-type="fig" rid="fig1">Figure 1</xref>5 represents the Cole-Cole plot of various Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> ferrites. It is noticed that the first two compositions (x = 0.0 and 0.1) show two semicircular arcs one at high frequency for grain interior and another at a lower frequency for grain boundary effect. The rest of the compositions show a single semicircular arc that specifies the materials have only grain contribution to the conduction process as the semicircle appearing at higher frequency correlates to the resistance of grain only but the semicircle at low frequency is because of the resistance of grain boundaries [<xref ref-type="bibr" rid="scirp.108005-ref36">36</xref>]. The grain boundary impedance arises due to the random alignment of grains existing two-dimensional conductivity. The non-existence of grain boundary impedance for x = 0.2, 0.3, and 0.4 may be due to the presence of the second phase dispersed along the grain boundary area which efficiently short</p><p>circuits the grain boundary impedance. Depressed semicircular arcs are perceived for every composition. Experimentally it is unusual to find a complete semicircle with its center lying on the axis of the Z'. The agitations which result in depressed semicircular arcs in the Z' axis are: 1) the arcs do not go through the origin because of the presence of other arcs at high frequency and/or the bulk resistance is larger than zero, 2) the centers of the investigational arcs are often relocated below the real axis due to the occurrence of dispersed elements in the material–electrode arrangement [<xref ref-type="bibr" rid="scirp.108005-ref37">37</xref>]. Therefore the relaxation time (τ) is not single-valued and is spread constantly or separately across a mean τ m ( = ω m − 1 ) and 3) arcs might be considerably twisted by additional relaxations. The arcs at higher frequency side constitute bulk resistance and those at the lower frequency side constitute grain boundary resistance [<xref ref-type="bibr" rid="scirp.108005-ref38">38</xref>] [<xref ref-type="bibr" rid="scirp.108005-ref39">39</xref>]. These responses can be explained by an equivalent circuit comprising of two sub-circuits attached in series as depicted in <xref ref-type="fig" rid="fig1">Figure 1</xref>5(f) [<xref ref-type="bibr" rid="scirp.108005-ref39">39</xref>]. In general, the impedance is expressed as:</p><table-wrap id="table3" ><label><xref ref-type="table" rid="table3">Table 3</xref></label><caption><title> The ɛ', grain, and grain boundary resistances of various Mn<sub>0.5</sub>Ni<sub>0.1</sub>Zn<sub>0.4</sub>Fe<sub>2−x</sub>Cr<sub>x</sub>O<sub>4</sub> ferrites</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >Composition</th><th align="center" valign="middle" >x = 0.0</th><th align="center" valign="middle" >x = 0.1</th><th align="center" valign="middle" >x = 0.2</th><th align="center" valign="middle" >x = 0.3</th><th align="center" valign="middle" >x = 0.4</th></tr></thead><tr><td align="center" valign="middle" >ε' at 100 kHz</td><td align="center" valign="middle" >35</td><td align="center" valign="middle" >26</td><td align="center" valign="middle" >29</td><td align="center" valign="middle" >55</td><td align="center" valign="middle" >316</td></tr><tr><td align="center" valign="middle" >R<sub>g</sub>(KΩ)</td><td align="center" valign="middle" >1009</td><td align="center" valign="middle" >1009</td><td align="center" valign="middle" >899</td><td align="center" valign="middle" >224</td><td align="center" valign="middle" >110</td></tr><tr><td align="center" valign="middle" >R<sub>gb</sub>(KΩ)</td><td align="center" valign="middle" >3267</td><td align="center" valign="middle" >3250</td><td align="center" valign="middle" >0</td><td align="center" valign="middle" >0</td><td align="center" valign="middle" >0</td></tr></tbody></table></table-wrap><p>Z * = R g − 1 / j w C g + R g b − 1 / j w C g b (11)</p><p>where R<sub>g</sub> is the grain resistance, C<sub>g</sub> is the grain capacitance, R<sub>gb</sub> is the grain boundary resistance and C<sub>gb</sub> is the grain boundary capacitance. The arcs in low and high-frequency areas conform to R<sub>gb</sub>C<sub>gb</sub> and R<sub>g</sub>C<sub>g</sub> responses, respectively. The grain resistance decreases rapidly with the rise in Cr<sup>3+</sup> in the composition (<xref ref-type="table" rid="table3">Table 3</xref>) due to the increased space charge polarization.</p></sec></sec><sec id="s4"><title>4. Conclusion</title><p>The XRD patterns identified a single-phase spinel ferrite structure. The FESEM images revealed that the D &#175; of the samples increased up to x = 0.2 owing to the development of Cr<sub>2</sub>O<sub>3</sub> liquid phase which promoted the grain growth and after x = 0.2, D &#175; decreased due to the shrinkage of the lattice. Among the studied samples, it is clear that 10% of Cr<sup>3+</sup> doped sample has the highest ɛ' with low loss, highest AC resistivity, good magnetizing capability, and highest RQF. The well saturated magnetic hysteresis loop indicated the ferromagnetic character of the present samples. The T<sub>C</sub> is found to be decreased with Cr content in the composition resulting from the smaller ionic radius of Cr than Fe. The impedance spectra analysis established a close correlation of the conduction mechanism with the microstructure of the samples. Both grain and grain boundaries contributed to the total conduction process for the first two compositions. The rest of the compositions had only grain contribution to the conduction process because the second phase dispersed along the grain boundary area efficiently short-circuited the grain boundary impedance. As in the field of electronics and communication devices have to deal with electric as well as magnetic properties, this ferrite composition may be used for the fabrication of different electronic and communication devices.</p></sec><sec id="s5"><title>Acknowledgements</title><p>The authors are thankful to the Dept. of Physics, Comilla University, Cumilla; Atomic Energy Centre, Dhaka (AECD), and Ministry of Science and Technology, Government of the People’s Republic of Bangladesh.</p></sec><sec id="s6"><title>Conflicts of Interest</title><p>The authors declare no conflicts of interest regarding the publication of this paper.</p></sec><sec id="s7"><title>Cite this paper</title><p>Haque, S., Mazumdar, S.C., Khan, M.N.I. and Das, M.K. (2021) Impact of Cr Substitution on Structural, Magnetic, Electric and Impedance Study of Mn-Ni-Zn Ferrites. Materials Sciences and Applications, 12, 121-138. https://doi.org/10.4236/msa.2021.123008</p></sec></body><back><ref-list><title>References</title><ref id="scirp.108005-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">Mazumdar, S.C., Khan, M.N.I., Islam, M.F. and Hossain, A.K.M.A. (2016) Tuning of Magnetoelectric Coupling in (1-y)Bi0.8Dy0.2FeO3-yNi0.5Zn0.5Fe2O4 Multiferroic Composites. Journal of Magnetism and Magnetic Materials, 401, 443-454. https://doi.org/10.1016/j.jmmm.2015.10.051</mixed-citation></ref><ref id="scirp.108005-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">Das, M.K., Zubair, M.A., Tanaka, H. and Hossain, A.K.M.A. (2020) Study of Impedance and Magnetoelectric Property of Lead-Free xLCNZFO+(1-x)BGTDO Multiferroic Composites. 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