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Influence of Ce3+ substitution on the structural, electrical and magnetic properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites
Journal Pre-proof Influence of Ce3+ substitution on the structural, electrical and magnetic Properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites
Salma Ikram, Jolly Jacob, K. Mahmood, A. Ali, N. Amin, U. Rehman, M. Imran Arshad, M. Ajaz un Nabi, Kashif Javid, A. Ashfaq, M. Sharif, S. Hussain PII:
S0921-4526(19)30663-5
DOI:
https://doi.org/10.1016/j.physb.2019.411764
Reference:
PHYSB 411764
To appear in:
Physica B: Physics of Condensed Matter
Received Date:
18 July 2019
Accepted Date:
08 October 2019
Please cite this article as: Salma Ikram, Jolly Jacob, K. Mahmood, A. Ali, N. Amin, U. Rehman, M. Imran Arshad, M. Ajaz un Nabi, Kashif Javid, A. Ashfaq, M. Sharif, S. Hussain, Influence of Ce3+ substitution on the structural, electrical and magnetic Properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites, Physica B: Physics of Condensed Matter (2019), https://doi.org/10.1016/j.physb. 2019.411764
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Influence of Ce3+ substitution on the structural, electrical and magnetic Properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites Salma Ikram1, Jolly Jacob2,K. Mahmood1*, A. Ali1, N. Amin1, U. Rehman1, M. Imran Arshad1, M. Ajaz un Nabi1, Kashif Javid1, A. Ashfaq1, M. Sharif1, S. Hussain3 1.Department of Physics, Government College University Faisalabad, Pakistan 2. College of Arts and Science, Abu Dhabi University, Abu Dhabi, UAE 3. Department of Physics, Division of Science and Technology, University of Education Lahore, Pakistan [email protected]
In this paper, the effect of Ce3+ ions addition on the microstructure, electrical and magnetic behaviour of Cadmium doped Mn-Zn ferrites was investigated. A series having composition Zn0.5Mn0.43Cd0.07Fe2-yCeyO4 (y=0.0-0.7) was synthesized by wet chemical route. X-Ray Diffraction (XRD) analysis showed that prepared particles having size in nano-regime having cubic spinel structure with preferred (311) plane. Weakening of (311) plane intensity and emergence of secondary phase with Ce3+ ion concentration verified the substitution of Ce3+ ions in the spinel lattice of ferrite. The crystallite size varied between 46.4-67 nm as the concentration of Ce3+ ions increased from x=0.0-0.7. Temperature and composition dependent electrical resistivity and activation energy values were calculated by current-voltage (I-V) characteristics in the temperature range 423 to 823K by two probe method. It was observed that DC Resistivity and activation energy of synthesized nanoparticle ranges between109 to ~1010 Ohm cm and 11.78-2.56 eV respectively with increasing the concentration of Ce3+ ions. MH curves of prepared samples showed the paramagnetic nature of spinel feerites. The reported data suggested that these particles promising candidates for high-frequency applications. Keywords; Cerium substituted Mn-Zn-Cd ferrites, Co-Precipitation method, XRD, DC electrical resistivity, M-H loop
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1. Introduction: Current electronic industry demands materials which posses both magnetic and ferroelectric properties simultanously. It is accepted fact that microscopic mechanism of both magnetism and ferroelectricity are entirely different processes and do not co-exist in a single material. Even in multiferroic materials where it is supposed that both properties can co-exists, there is no strong coupling evidence between these two properties which cause a hurdle to use such materials in commercial applications. On the other hand, Ferrites materials are gaining great fundamental and technological importance because above mentioned phenomenons are not only co-exists but strongly couples as well. Furthermore, Spinel ferrites also posses some interesting properties such as high values of magnetic permeability, high chemical stability, tuneable shape and size, low Coercivity along with high electrical resistivities [1, 2]. In this class of ferries, Mn-Zn spinal ferrites are emerging as potential candidates for many technological applications due to their ferromagnetic and semiconducting nature. Mn-Zn ferrites can be operated at high-frequencies because they have low power losses and posses high values of magnetic permeability [3]. Intrestingly, we can further improve the structural, electrical and magnetic properties of such materials by the substitution of Fe3+ with suitable foreign atoms [4, 6]. Effect of various ions such as Cd3+, Sm3+, Gd3+ and La3+ doping on the different properties of Mn-Zn ferrites have been studied in the literature, but Ce3+ ions substitution in Cd-Mn-Zn ferrites has not been reported in the literature according to best of our knowledge [7-9]. Furthermore, an appropriated method for synthesis of Ce3+ substituted spinel ferrites can give a better control to achieve required electrical and magnetic parameters for particular applications [10]. In this research work, the effect of Ce3+ ions substitution on microstructure, electrical and magnetic properties of Cadmium doped Mn-Zn nanoferrites was investigated. The Co-
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precipitated synthesized nano-particles were characterized by XRD, FTIR, DC resistivity and magnetic measurements. The effect of Ce3+ ions substitution on the various structural parameters including crystallite size, lattice parameter and cell volume was calculated and reported in this paper. Finally the effect of Ce3+ ions substitution on DC electrical resistivity and various magnetic parameters was also investigated in detailed. 2. Methodology The samples used in this study were prepared by co-precipatation method. Various source salts such as MnCl2.4H2O, ZnCl2.6H2O, CdCl2.2.5H2O,CeCl3.7H2O, and FeCl3 having purity 99.9% were dissolved in de-ionized water and mixed as per stoichiometric ratios. The mixed solutions were magnetically stirrered at moderate speed of 50 rpm using magnetic stirrer. To keep pH of solutions constant at 11.3 Molar, NaOH solution was added drop wise into the host solutions during stirrering. All solutions (after maintaining pH at 11) were transfered into a pre heated water bath at temperature 358 K for two hours. During this digestion process, the particles were settled at the bottom of beakers. The solutions were filtered after cooling to room temperature and prepared ferrite material was collected from filter paper. Electric oven at 343K was used to dry the prepared ferrite materials. Finally the material was grinded and in powder form the fine particles were obtained [11,12]. The prepared particles were annealed at 1173K and characterized by XRD for structure analysis, FTIR for bonding verification and VSM for the study of magnetic properties. All these measurements were performed at room temperature. Current-Voltage (IV) characteristics of synthesized nanoparticles were measured in the temperature range 423-823 K using Keithly 2401 current-voltage meter.
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3. Results and discussions 3.1. Structural aanalysis Fig. 1 shows the representative X-ray diffraction patterns of Ce3+ substituted Cd based Mn-Zn ferrites (Zn0.5Mn0.43Cd.07Fe2-yCeyO4, y= 0.0-0.7) prepared by chemical co-precipitation method. We have observed six diffraction peaks at angles 2θ=29.940, 35.260, 42.880, 53.010, 56.60 correspond to hkl planes (220), (311), (222), (422) and (511) respectively which are in good agreement with the JCP card number COD 2009103. The XRD data confirmed the single-phase cubic spinel structure of grown nanoparticles. It is observed that with increasing the concentration of Ce3+ ions in the spinel lattice of ferrite, the intensity of (311) plane decreases meanwhile intensity of peak correspond to a plane (111) increases along with the emergence of CeO2 secondary phase. This behavior may be due to the larger ionic radii of Ce3+ ions compared to Fe3+. It is also observed that crystallinity of synthesized nanoparticles decreases with increasing Ce3+ ions concentration because the potential barrier increases with dopant concentrations that Ce3+ ion has to overcome for entering the spinel crystal lattice which resulted in crystal lattice distortions and local strain [13,14]. Table 1 depicted that particle size of all samples calculated using the most intense plane (311) shows a nonlinear behavior with increasing concentration of Ce3+ ions. It increases initially (from x=0 to x=0.1) due the fact that atoms with smaller ionic radii Fe3+ (0.064 nm) were replaced by larger ionic radii Ce3+ (0.115 nm) atoms. But the further increment of Ce3+ concentration (x=0.1, x=0.2) resulted in the reduction of particle size due to the development of secondary phase which led to the shrinkage of lattice. The other reasons for the decrease of particle size are may be the lattice strains which arise due to the high concentration of Cerium metal ions and emergence of secondary phase as well [15].
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The value of lattice parameter ‘a’ was calculated for all samples and tabulated in Table 1. The data demonstrated that lattice constant first increase than decreases. The increase in lattice parameter may be due to the fact that smaller radii (Fe3+) ion is replaced with an atom having larger radii (Ce3+) with values 0.115 nm and 0.23 nm respectively. For higher concentration of Ce3+ ions the decreasing trend of lattice constant could be explained as; Ce3+ ions may replace Fe3+ ions from octahedral sites rather than tetrahedral sites because tetrahedral sites are too small to accommodate Ce3+ ions. So instead of entering into the spinel lattice, Ce3+ ions may diffuse into the grain boundaries which produced lattice strain resulting in shrinkage of spinel lattice [16]. Using standard formulas we have also calculated X-Ray density, bulk density and porosity of all samples and are listed in Table 1. Both x-ray density and bulk density were found to be increased with increasing concentration of Ce3+ ions. Bulk density has value less than x-ray density due to the formation of pores and voids during annealing [17]. Porosity of prepared materials decreases with the increasing concentration of Ce3+ ions. This decreasing trend attributes to smaller values of bulk density as compare to x-ray density [18]. 3.2. FTIR FTIR spectra of synthesized Ce3+ substituted MnZnCd nano-ferrites grown by co-precipatation method and annealed at 1173K is shown in fig. 2. Typical FTIR spectra for ferrites normally consisted of two peaks which are the typical characteristics bands of ferrites. FTIR data in fig. 2 demonstrated two bands, the tetrahedral complexes bands appeared at high wave numbers (v1= ̴530-560cm-1) and the octahedral complexes band appeared at low wave numbers (𝑣2= 430-448 cm-1). This behaviour further confirmed the formation of spinel structure of prepared nanoferrites and strengthened the XRD results. Furthermore, the vibration of Fe3+-O2- in the sublattice site A is represented by high wave number band 𝑣1While at the octahedral B-site, lower wave number
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band 𝑣2 represents the M-O vibration [19,20]. The values of force constants Kt and Ko for tetrahedral and octahedral sites were calculated by following relations; Ko = 0.942 (ʋ2)2M / (32+ M)
(1)
Kt =Ko √2 ʋ1 / ʋ2
(2)
The effect of substitution of Ce3+ on values of 𝑣1,𝑣2, force constants Kt and Ko and radii of octahedral and tetrahedral sites Ro and Rt is summarized in table 2. 3.3. I-V Characteristis To calculate the resistivity of synthesized nanoparticles, we have performed current-voltage characteristics in the temperature range 423 to 823K. DC resistivity of prepared nano-ferrites was calculated using following well known formula; ρ = RA/L
(3)
Where ρ is electrical resistivity, A is the area of the pallet and L is the thickness of the pallet [21] and R is the resistance of the nanoferrites obtained from the slop of I-V curves. The effect of measurement temperature on the electrical resistivity is shown in fig. 3. The graph demonstrated that electrical resistivity decreases for all samples as the measurement temperature increases from 450-800K which is the characteristic behavior of resistivity for ferrite materials. The hopping conduction is supposed to the origin of this conduction which strongly related to the temperature, but other factors such as material’s density and porosity, composition, particle size, annealing temperature and growth technique are also possible factors for conduction [22-24]. But temperature is the most dominant factor because at high measurement temperature, carriers gain thermal energy and jump from defect site to another. This movement of carriers cause very small
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conduction. The data also suggested that electrical resistivity increased from1.18 x108 Ω-cm to 9.06 x 108 Ω-cm as the dopant concentration increased from x=0 to x=0.7 respectively. It might be due to the decrease of Fe3+ ions at tetrahedral sites and also due to creation of distortion in the crystal by substitution of Ce3+ which disturb the hoping conduction and consequently decreased the resistivity [25]. From the slop of lnρ versus 1000/T graph, the activation energy of prepared nanoparticles was calculated and it was found to lie in the range 0.08-0.1 eV (fig. 4). Such low value of activation energy is due the hopping conduction nature of defects in the grown samples. This activation energy values are also supported our resistivity data that conduction in grown ferrites is due to hopping mechanisms [26]. 3.4. Magnetic Measurements Fig. 5 depicts the effect of Ce3+ ions substitution on the magnetic properties (M-H loop) of MnZn-Cd ferrites synthesized by co-precipitation method. From these curves it is clear that saturation magnetization for sample having Ce+3 concentration x= 0.3 posses the highest value. We have also observed a random variation of saturation magnetization as the concentration of Ce+3 ions increased. This variation is linked with the variation of particle size of the synthesized nanomaterials. It is clear from the M-H curves that increase in Ce3+contents, paramagnetic behavioralso increases due to the paramagnetic nature of Ce3+ ions [27]. The value of saturation magnetization Ms is lower than the previous quoted values for pure MnZnCd Fe2O4 ferrites. This low value of coecivity was further decreased with increasing concentration of Ce3+ ions. This change may be attributed to the paramagnetic nature of Cerium metal ions and their magnetic moments.
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To study the effect of nanosized domain on magnetic properties, the values of squareness ratio (Mr/Ms) from the MH curves were calculated. The prepared nanoferrites have squrance ratio below 0.5 and lies in the range 0.012-0.044 which shows the single domain behaviour of prepared nanoferrites [28]. The magnetic moment nB per formula unit in Bohr magnetron andmagnetocrystalline anisotropy constant was calculated as K1=MsHc/ 2
(4)
nB (µB) = MsM / 5585
(5)
Where Hc is the Coercivity, M is molecular weight of prepared materials, Ms is the saturation magnetization and µo is the permeability of free space. Table 3 shows that calculated anisotropy values lies in the range 23.27- 141.84 J/m3. These high values of anisotropy constant predict that the anisotropy contribution may not be uniaxial [29-31]. The calculated values of magnetic moments are proportional to saturation magnetization and increases linearly with Ce3+ concentration. Particle size (D), saturation magnetization (Ms) and initial permeability (µi) is interlinked by the following relation[32]. µi = Ms2 D/ K1
(6)
Here k1 is the anisotropy constant. Relation between Ce3+ concentration and initial permeability could be observed in table 3. Linear relationship between µi and grain size was reported previously by Reddy et al [33].
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4. Conclusion In this research paper, we have synthesized Ce3+ substituted Mn-Zn-Cd nanoferrites by coprecipitation method and investigated the influence of Ce3+ ions substitution on the structural, electrical and magnetic properties of grown samples. XRD results showed that the synthesized nanoferrites belongs to fd3m space group.The particle size of these synthesized ferrites lies in the nano regime and found to be decreased by increasing the substitution of Ce3+ ions. FTIR spectra has confirmed the spinel structure of synthesized nanoferrites. Electrical resistivity of these nanoparticles increases with increasing Ce3+ concentration. M-H curves clearly showed the paramagnetic nature and single domain behavior of synthesized samples. All observed properties suggested that these nanoparticles are special candidates for high frequency devices and magnetic recording media. References [1] M. S. Hasan, M. I. Arshad, A. Ali, K. Mahmood, N. Amin, S. S. Ali, M. Saleem, Mg and La co-doped ZnNi spinel ferrites for low resistive applications, Materials Research Express. 6 (2018) 016302. [2] M. Arshad, N. Amin, M. Islam, A. Ali, K. Mahmood, M. Nabi, G. Mustafa, Effects of srsubstitution on the microstructure and magnetic behavior of m-type hexagonal ferrites synthesis by co-precipitation method, Journal of ovonic research. 13 (2017) 203-210. [3] S. Ikram, M. I. Arshad, K. Mahmood, A. Ali, N. Amin, N. Ali, Structural, magnetic and dielectric study of La3+ substituted Cu0.8Cd0.2Fe2O4 ferrite nanoparticles synthesized by the coprecipitation method, Journal of Alloys and Compounds. 769 (2018) 1019-1025.
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[4] I. Ahmad, M. Ahmad, I. Ali, M. Kanwal, M. S. Awan, G. Mustafa, M. Ahmad, Effects of Gd-substitutions on the microstructure, electrical and electromagnetic behavior of M-type hexagonal ferrites, Journal of Electronic Materials. 44 (2017) 2221-2229. [5] M. S. Hasan, M. I. Arshad, A. Ali, K. Mahmood, N. Amin, S. S. Ali, M. Saleem, Mg and La co-doped ZnNi spinel ferrites for low resistive applications, Materials Research Express. 6 (2018) 016302. [6] G. Mustafa, M. U. Islam, W. Zhang, Y. Jamil, A. W. Anwar, M. Hussain, M. Ahmad, Investigation of structural and magnetic properties of Ce3+-substituted nanosized Co–Cr ferrites for a variety of applications, Journal of Alloys and Compounds. 618 (2015) 428-436. [7] S. Ikram, J. Jacob, M. I. Arshad, K. Mahmood, A. Ali, N. Sabir, S. Hussain, Tailoring the Structural, Magnetic and Dielectric properties of Ni-Zn-CdFe2O4 spinel ferrites by the substitution of Lanthanum ions, Ceramics International. 45 (2019) 3563-3569. [8] R. Gimenes, M. D. Baldissera, M. R. A. Da Silva, C. A. Da Silveira, D. A. W. Soares, L. A. Perazolli, M. A. Zaghete, Structural and magnetic characterization of MnxZn1−xFe2O4 (x= 0.2; 0.35; 0.65; 0.8; 1.0) ferrites obtained by the citrate precursor method, Ceramics international. 38 (2012) 741-746. [9] V. J. Angadi, B. Rudraswamy, K. Sadhana, S. R. Murthy, K. Praveena, Effect of Sm3+– Gd3+ on structural, electrical and magnetic properties of Mn–Zn ferrites synthesized via combustion route, Journal of Alloys and Compounds. 656 (2016) 5-12.
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[10] N. Amin, M. I. Arshad, M. U. Islam, A. Ali, K. Mahmood, G. Murtaza, G. Mustafa, Role of y3+ ions on the structural and dielectric properties of Ni-Zn-Cr ferrites synthesized by coprecipitation method, Digest Journal of Nanomaterials and Biostructures. 11 (2016) 579-590. [11] M. A. Khan, M. J. ur Rehman, K. Mahmood, I. Ali, M. N. Akhtar, G. Murtaza, I. Shakir, M. F. Warsi, Impacts of Tb substitution at cobalt site on structural, morphological and magnetic properties of cobalt ferrites synthesized via double sintering method, Ceramics International. 41 (2015) 2286-2293. [12] M. Y. Lodhi, K. Mahmood, A. Mahmood, H. Malik, M. F. Warsi, I. Shakir, M. A. Khan, New Mg0.5CoxZn0.5−xFe2O4 nano-ferrites: structural elucidation and electromagnetic behavior evaluation, Current Applied Physics. 14 (2014) 716-720. [13] H. Malik, A. Mahmood, K. Mahmood, M. Y. Lodhi, M. F. Warsi, I. Shakir, M. A. Khan, Influence of cobalt substitution on the magnetic properties of zinc nanocrystals synthesized via micro-emulsion route, Ceramics International. 40 (2014) 9439-9444. [14] G. Mustafa, M. U. Islam, W. Zhang, A. W. Anwar, Y. Jamil, G. Murtaza, M. Ahmad, Influence of the divalent and trivalent ions substitution on the structural and magnetic properties of Mg0.5−xCdxCo0.5Cr0.04TbyFe1.96− yO4 ferrites prepared by sol–gel method, Journal of Magnetism and Magnetic Materials. 387 (2015) 147-154. [15] D.Ravinder, Far-infrared spectral studies of mixed Lithium-Zinc ferrites, Mater. Letter. 1016 (1999) 205-208. [16] B. Baruwati, K. M. Reddy, S. V. Manorama, R. K. Singh, O. Parkash, Tailored conductivity behavior in nanocrystalline nickel ferrite, Applied physics letters. 85 (2004) 2833-2835.
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[17] I. H. Gul, A. Maqsood, Structural, magnetic and electrical properties of cobalt ferrites prepared by the sol–gel route, Journal of Alloys and Compounds. 465 (2008) 227-231. [18] I. H. Gul, W. Ahmed, A. Maqsood, Electrical and magnetic characterization of nanocrystalline Ni–Zn ferrite synthesis by co-precipitation route, Journal of Magnetism and Magnetic Materials. 320 (2008) 270-275. [19] E. Rezlescu, L. Sachelarie, P. D. Popa, N. Rezlescu, Effect of substitution of divalent ions on the electrical and magnetic properties of Ni-Zn-Me ferrites, IEEE transactions on magnetics. 36 (2000) 3962-3967. [20] R. Zahra, K. Mahmood, A. Ali, U. Rehman, N. Amin, M. I. Arshad, M. H. Mahmood, Growth of Zn2GeO4 thin film by thermal evaporation on ITO substrate for thermoelectric power generation applications, Ceramics International. 45 (2019) 312-316. [21] A. A. Kadam, S. S. Shinde, S. P. Yadav, P. S. Patil, K. Y. Rajpure, Structural, morphological, electrical and magnetic properties of Dy doped Ni–Co substitutional spinel ferrite, Journal of Magnetism and Magnetic materials. 329 (2013) 59-64. [22] R. Mohamed, M. M. Rashad, F. A. Haraz and W. Sigmund, Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method, J. mag. magn. Mater. 322 (2010) 2058-2064. [23] Arslan Ashfaq, J. Jacob, N. Bano, A. Ali, W. Ahmad, K. Mahmood, M I Arsha, S. Ikram, U. Rehman, S. Hussain, Tailoring the thermoelectric properties of sol-gel grown CZTS/ITO thin films by controlling the secondary phases, Physica B. 558 (2019) 86. [24] S. S. Abbas, I. H. Gul, S. Ameer, M. Anees, Ce-Substituted Co0.5Ni0.5Fe2O4: Structural, Morpphological, Electrical, and Dielectric Properties, Electron matter. 100 (2015) 100-108.
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[25] E. Pervaiz, I. H. Gul, High frequency AC response, DC resistivity and magnetic studies of holmium substituted Ni-ferrite: a novel electromagnetic material, Journal of magnetism and magnetic materials. 349 (2014) 27-34. [26] Z. Peng, X. Fu, H. Ge, Z. Fu, C. Wang, L. Qi, H. Miao, Effect of Pr3+ doping on magnetic and dielectric properties of Ni–Zn ferrites by one-step synthesis, J. Mag. Magn. Mater. 323, (2011) 2513-2518. [27] J. H. Nam, H. H. Jung, J. Y. Shin, J. H. Oh, The effect of Cu substitution on the electrical and magnetic properties of NiZn ferrites. IEEE Transactions on Magnetics, 31 (1995) 39853987. [28] C. B. Kolekar, P. N. Kamble, A. S. Vaingankar, Structural and dc electrical resistivity study of Gd3+-substituted Cu-Cd mixed ferrites, Journal of magnetism and magnetic materials. 138 (1994) 211-215. [29] M. Sugimoto, The past, present, and future of ferrites, Journal of the American Ceramic Society. 82 (1999) 269-280. [30] C. Venkataraju, G. Sathishkumar, K. Sivakumar, Effect of Cd on the structural, magnetic and electrical properties of nanostructured Mn–Zn ferrite, Journal of Magnetism and Magnetic Materials. 323 (2011) 1817-1822. [31] W. A. Wooster, Physical properties and atomic arrangements in crystals, Reports on Progress in Physics. 16 (1953) 62. [32] B. Baruwati, K. M. Reddy, S. V. Manorama, R. K. Singh, O. Parkash, Tailored conductivity behavior in nanocrystalline nickel ferrite, Applied physics letters. 85 (2004) 2833-2835.
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[33] C. G. Reddy, S. V. Manorama, V. J. Rao, Semiconducting gas sensor for chlorine based on inverse spinel nickel ferrite, Sensors and Actuators B: Chemical. 55 (1999) 90-95. List of Figures and Tables: Figure 1:- XRD diffractograms of Mn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites with different concentration of Ce3+ ions . Figure 2:- Room temperature FTIR spectra of Mn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites (where y= 0.0 - 0.7). Figure 3:- Plot between resistivity and temperature of synthesized Mn0.43Zn0.5 Cd.07Cey Fe2-y O4 nanoferrites (where y= 0.0 - 0.7). Figure 4:- Plot between lnρ and 1000/T of synthesizedMn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites (where y= 0.0 - 0.7). Figure 5:- The MH- loop for Mn0.43Zn0.5 Cd.07Cey Fe2-y O4(y= 0.1, 0.3, 0.5) nanoferrites Table 1:- Effect of Ce3+ substitution on Crystallite size (D), Lattice constant (ɑ) and Cell volume (Vcell),
packing
factor,
x-ray
density,
bulk
density
and
porosity
of
synthesized
Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites. Table 2:- Effect of Ce3+ substitution on high frequency band (ʋ1), low frequency band (ʋ2), Rt, Ro, and force constants Kt and Ko ofsynthesized Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites. Table 3:- Effect of Ce3+ substitution on saturation magnetization (Ms), remanence (Mr), coercivity (Hc), squarance ratio, anisotropy constant K1 and bohar magneton nB(µB) ofsynthesized Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites.
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Figure 1
y =0.7
intensity (a.u)
y =0.5
y =0.3 y =0.2
y=0.1
y = 0.0 20
25
30
35
40
2 Theta (degree)
45
50
55
60
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Figure 2
Transmittence (%)
y=0.7
y=0.5 y=0.3 y=0.1 y=0.0
800
750
700
650
600
Wave number cm-1
550
500
450
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Fig. 3
10
6x10
10
Resistivity (Ohm-Cm)
5x10
y = .7
10
4x10
y = .5
10
y = .4
10
y = .3
3x10
2x10
y= .2
10
1x10
y = .1 250
300
350
400
450
500
Temperature (K)
550
600
650
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Fig. 4
60
y= 0.7 y= 0.5 50
ln cm)
y = 0.4 y = 0.3
40
y = 0.2 30
y = 0.1
20
1.5
2.0
2.5
3.0 -1
1000/T (K )
3.5
4.0
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Fig. 5
0.04
y= .1 y= .3 y= .5
Magnatization (emu/g)
0.03 0.02 0.01 0.00 -0.01 -0.02 -0.03 -0.04
-30000
-20000
-10000
0
10000
Magnetic Field (Oe)
20000
30000
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Table 1 y
0.0
Lattice Constant ‘a’
Cell volume
(Ǻ)
(Ǻ3)
‘a3’
Particle size ‘t’
Packing Factor
x-ray density
Bulk density
(nm)
P
ρx (g/cm3)
ρm (g/cm3)
Porosity %
8.437269
600.6281
43.1274186
169.5305277
5.304532
3.84741
27.46937
8.437269
600.6281
42.685562
167.7936235
5.490986
3.94284
28.1943
8.43032
599.1454
38.26144
150.5267164
5.69149
4.054414
28.76358
8.425694
598.1596
41.7944036
164.5162419
5.887871
4.173092
29.12393
8.448877
603.1106
46.5056932
182.5590935
6.210909
4.912555
20.90441
8.421074
597.1761
41.3816624
162.9809366
6.647472
5.10624
23.18523
ʋ1
ʋ2
Rt
Ro
Kt
Ko
(cm-1)
(cm-1)
(Ǻ)
(Ǻ)
(erg/cm3)
(erg/cm3)
0.0
543.18
452.28
0.476669
0.759317
170032.4
287930.2
0.1
544.04
456.74
0.476669
0.759317
174098.3
292398.7
0.3
542.66
451.19
0.474163
0.756424
171134.9
290219.1
0.5
541.98
450.66
0.479182
0.762219
171839.7
291391.6
0.7
541.18
449.76
0.473162
0.755268
172143.4
292058.9
0.1 0.2 0.3 0.5 0.7
Table 2 y
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Table 3 Y
Saturaton magnetizatio n Ms (emu/g)
Remanence Mr (emu/g)
Coercivit y Hc (Oe)
Mr / Ms
Anisotropy constant K1 (J/m3)
Initial permeability µi
nB(µB)
0.1
22.98
1.02
12.345
0.04438
141.8441
158.5982989
1.0214
0.3
24.62
0.34
4.07
0.01381
50.1017
504.4982801
1.1686
0.5
18.22
0.22
2.555
0.01207
23.27605
663.1937378
0.9198
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Declaration of interests ☐The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
I confirmed above both statements
Salma Ikram, Jolly Jacob, K. Mahmood, A. Ali, N. Amin, U. Rehman, M. Imran Arshad, M. Ajaz un Nabi, Kashif Javid, A. Ashfaq, M. Sharif, S. Hussain PII:
S0921-4526(19)30663-5
DOI:
https://doi.org/10.1016/j.physb.2019.411764
Reference:
PHYSB 411764
To appear in:
Physica B: Physics of Condensed Matter
Received Date:
18 July 2019
Accepted Date:
08 October 2019
Please cite this article as: Salma Ikram, Jolly Jacob, K. Mahmood, A. Ali, N. Amin, U. Rehman, M. Imran Arshad, M. Ajaz un Nabi, Kashif Javid, A. Ashfaq, M. Sharif, S. Hussain, Influence of Ce3+ substitution on the structural, electrical and magnetic Properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites, Physica B: Physics of Condensed Matter (2019), https://doi.org/10.1016/j.physb. 2019.411764
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Influence of Ce3+ substitution on the structural, electrical and magnetic Properties of Zn0.5Mn0.43Cd0.07Fe2O4 spinel ferrites Salma Ikram1, Jolly Jacob2,K. Mahmood1*, A. Ali1, N. Amin1, U. Rehman1, M. Imran Arshad1, M. Ajaz un Nabi1, Kashif Javid1, A. Ashfaq1, M. Sharif1, S. Hussain3 1.Department of Physics, Government College University Faisalabad, Pakistan 2. College of Arts and Science, Abu Dhabi University, Abu Dhabi, UAE 3. Department of Physics, Division of Science and Technology, University of Education Lahore, Pakistan [email protected]
In this paper, the effect of Ce3+ ions addition on the microstructure, electrical and magnetic behaviour of Cadmium doped Mn-Zn ferrites was investigated. A series having composition Zn0.5Mn0.43Cd0.07Fe2-yCeyO4 (y=0.0-0.7) was synthesized by wet chemical route. X-Ray Diffraction (XRD) analysis showed that prepared particles having size in nano-regime having cubic spinel structure with preferred (311) plane. Weakening of (311) plane intensity and emergence of secondary phase with Ce3+ ion concentration verified the substitution of Ce3+ ions in the spinel lattice of ferrite. The crystallite size varied between 46.4-67 nm as the concentration of Ce3+ ions increased from x=0.0-0.7. Temperature and composition dependent electrical resistivity and activation energy values were calculated by current-voltage (I-V) characteristics in the temperature range 423 to 823K by two probe method. It was observed that DC Resistivity and activation energy of synthesized nanoparticle ranges between109 to ~1010 Ohm cm and 11.78-2.56 eV respectively with increasing the concentration of Ce3+ ions. MH curves of prepared samples showed the paramagnetic nature of spinel feerites. The reported data suggested that these particles promising candidates for high-frequency applications. Keywords; Cerium substituted Mn-Zn-Cd ferrites, Co-Precipitation method, XRD, DC electrical resistivity, M-H loop
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1. Introduction: Current electronic industry demands materials which posses both magnetic and ferroelectric properties simultanously. It is accepted fact that microscopic mechanism of both magnetism and ferroelectricity are entirely different processes and do not co-exist in a single material. Even in multiferroic materials where it is supposed that both properties can co-exists, there is no strong coupling evidence between these two properties which cause a hurdle to use such materials in commercial applications. On the other hand, Ferrites materials are gaining great fundamental and technological importance because above mentioned phenomenons are not only co-exists but strongly couples as well. Furthermore, Spinel ferrites also posses some interesting properties such as high values of magnetic permeability, high chemical stability, tuneable shape and size, low Coercivity along with high electrical resistivities [1, 2]. In this class of ferries, Mn-Zn spinal ferrites are emerging as potential candidates for many technological applications due to their ferromagnetic and semiconducting nature. Mn-Zn ferrites can be operated at high-frequencies because they have low power losses and posses high values of magnetic permeability [3]. Intrestingly, we can further improve the structural, electrical and magnetic properties of such materials by the substitution of Fe3+ with suitable foreign atoms [4, 6]. Effect of various ions such as Cd3+, Sm3+, Gd3+ and La3+ doping on the different properties of Mn-Zn ferrites have been studied in the literature, but Ce3+ ions substitution in Cd-Mn-Zn ferrites has not been reported in the literature according to best of our knowledge [7-9]. Furthermore, an appropriated method for synthesis of Ce3+ substituted spinel ferrites can give a better control to achieve required electrical and magnetic parameters for particular applications [10]. In this research work, the effect of Ce3+ ions substitution on microstructure, electrical and magnetic properties of Cadmium doped Mn-Zn nanoferrites was investigated. The Co-
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precipitated synthesized nano-particles were characterized by XRD, FTIR, DC resistivity and magnetic measurements. The effect of Ce3+ ions substitution on the various structural parameters including crystallite size, lattice parameter and cell volume was calculated and reported in this paper. Finally the effect of Ce3+ ions substitution on DC electrical resistivity and various magnetic parameters was also investigated in detailed. 2. Methodology The samples used in this study were prepared by co-precipatation method. Various source salts such as MnCl2.4H2O, ZnCl2.6H2O, CdCl2.2.5H2O,CeCl3.7H2O, and FeCl3 having purity 99.9% were dissolved in de-ionized water and mixed as per stoichiometric ratios. The mixed solutions were magnetically stirrered at moderate speed of 50 rpm using magnetic stirrer. To keep pH of solutions constant at 11.3 Molar, NaOH solution was added drop wise into the host solutions during stirrering. All solutions (after maintaining pH at 11) were transfered into a pre heated water bath at temperature 358 K for two hours. During this digestion process, the particles were settled at the bottom of beakers. The solutions were filtered after cooling to room temperature and prepared ferrite material was collected from filter paper. Electric oven at 343K was used to dry the prepared ferrite materials. Finally the material was grinded and in powder form the fine particles were obtained [11,12]. The prepared particles were annealed at 1173K and characterized by XRD for structure analysis, FTIR for bonding verification and VSM for the study of magnetic properties. All these measurements were performed at room temperature. Current-Voltage (IV) characteristics of synthesized nanoparticles were measured in the temperature range 423-823 K using Keithly 2401 current-voltage meter.
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3. Results and discussions 3.1. Structural aanalysis Fig. 1 shows the representative X-ray diffraction patterns of Ce3+ substituted Cd based Mn-Zn ferrites (Zn0.5Mn0.43Cd.07Fe2-yCeyO4, y= 0.0-0.7) prepared by chemical co-precipitation method. We have observed six diffraction peaks at angles 2θ=29.940, 35.260, 42.880, 53.010, 56.60 correspond to hkl planes (220), (311), (222), (422) and (511) respectively which are in good agreement with the JCP card number COD 2009103. The XRD data confirmed the single-phase cubic spinel structure of grown nanoparticles. It is observed that with increasing the concentration of Ce3+ ions in the spinel lattice of ferrite, the intensity of (311) plane decreases meanwhile intensity of peak correspond to a plane (111) increases along with the emergence of CeO2 secondary phase. This behavior may be due to the larger ionic radii of Ce3+ ions compared to Fe3+. It is also observed that crystallinity of synthesized nanoparticles decreases with increasing Ce3+ ions concentration because the potential barrier increases with dopant concentrations that Ce3+ ion has to overcome for entering the spinel crystal lattice which resulted in crystal lattice distortions and local strain [13,14]. Table 1 depicted that particle size of all samples calculated using the most intense plane (311) shows a nonlinear behavior with increasing concentration of Ce3+ ions. It increases initially (from x=0 to x=0.1) due the fact that atoms with smaller ionic radii Fe3+ (0.064 nm) were replaced by larger ionic radii Ce3+ (0.115 nm) atoms. But the further increment of Ce3+ concentration (x=0.1, x=0.2) resulted in the reduction of particle size due to the development of secondary phase which led to the shrinkage of lattice. The other reasons for the decrease of particle size are may be the lattice strains which arise due to the high concentration of Cerium metal ions and emergence of secondary phase as well [15].
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The value of lattice parameter ‘a’ was calculated for all samples and tabulated in Table 1. The data demonstrated that lattice constant first increase than decreases. The increase in lattice parameter may be due to the fact that smaller radii (Fe3+) ion is replaced with an atom having larger radii (Ce3+) with values 0.115 nm and 0.23 nm respectively. For higher concentration of Ce3+ ions the decreasing trend of lattice constant could be explained as; Ce3+ ions may replace Fe3+ ions from octahedral sites rather than tetrahedral sites because tetrahedral sites are too small to accommodate Ce3+ ions. So instead of entering into the spinel lattice, Ce3+ ions may diffuse into the grain boundaries which produced lattice strain resulting in shrinkage of spinel lattice [16]. Using standard formulas we have also calculated X-Ray density, bulk density and porosity of all samples and are listed in Table 1. Both x-ray density and bulk density were found to be increased with increasing concentration of Ce3+ ions. Bulk density has value less than x-ray density due to the formation of pores and voids during annealing [17]. Porosity of prepared materials decreases with the increasing concentration of Ce3+ ions. This decreasing trend attributes to smaller values of bulk density as compare to x-ray density [18]. 3.2. FTIR FTIR spectra of synthesized Ce3+ substituted MnZnCd nano-ferrites grown by co-precipatation method and annealed at 1173K is shown in fig. 2. Typical FTIR spectra for ferrites normally consisted of two peaks which are the typical characteristics bands of ferrites. FTIR data in fig. 2 demonstrated two bands, the tetrahedral complexes bands appeared at high wave numbers (v1= ̴530-560cm-1) and the octahedral complexes band appeared at low wave numbers (𝑣2= 430-448 cm-1). This behaviour further confirmed the formation of spinel structure of prepared nanoferrites and strengthened the XRD results. Furthermore, the vibration of Fe3+-O2- in the sublattice site A is represented by high wave number band 𝑣1While at the octahedral B-site, lower wave number
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band 𝑣2 represents the M-O vibration [19,20]. The values of force constants Kt and Ko for tetrahedral and octahedral sites were calculated by following relations; Ko = 0.942 (ʋ2)2M / (32+ M)
(1)
Kt =Ko √2 ʋ1 / ʋ2
(2)
The effect of substitution of Ce3+ on values of 𝑣1,𝑣2, force constants Kt and Ko and radii of octahedral and tetrahedral sites Ro and Rt is summarized in table 2. 3.3. I-V Characteristis To calculate the resistivity of synthesized nanoparticles, we have performed current-voltage characteristics in the temperature range 423 to 823K. DC resistivity of prepared nano-ferrites was calculated using following well known formula; ρ = RA/L
(3)
Where ρ is electrical resistivity, A is the area of the pallet and L is the thickness of the pallet [21] and R is the resistance of the nanoferrites obtained from the slop of I-V curves. The effect of measurement temperature on the electrical resistivity is shown in fig. 3. The graph demonstrated that electrical resistivity decreases for all samples as the measurement temperature increases from 450-800K which is the characteristic behavior of resistivity for ferrite materials. The hopping conduction is supposed to the origin of this conduction which strongly related to the temperature, but other factors such as material’s density and porosity, composition, particle size, annealing temperature and growth technique are also possible factors for conduction [22-24]. But temperature is the most dominant factor because at high measurement temperature, carriers gain thermal energy and jump from defect site to another. This movement of carriers cause very small
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conduction. The data also suggested that electrical resistivity increased from1.18 x108 Ω-cm to 9.06 x 108 Ω-cm as the dopant concentration increased from x=0 to x=0.7 respectively. It might be due to the decrease of Fe3+ ions at tetrahedral sites and also due to creation of distortion in the crystal by substitution of Ce3+ which disturb the hoping conduction and consequently decreased the resistivity [25]. From the slop of lnρ versus 1000/T graph, the activation energy of prepared nanoparticles was calculated and it was found to lie in the range 0.08-0.1 eV (fig. 4). Such low value of activation energy is due the hopping conduction nature of defects in the grown samples. This activation energy values are also supported our resistivity data that conduction in grown ferrites is due to hopping mechanisms [26]. 3.4. Magnetic Measurements Fig. 5 depicts the effect of Ce3+ ions substitution on the magnetic properties (M-H loop) of MnZn-Cd ferrites synthesized by co-precipitation method. From these curves it is clear that saturation magnetization for sample having Ce+3 concentration x= 0.3 posses the highest value. We have also observed a random variation of saturation magnetization as the concentration of Ce+3 ions increased. This variation is linked with the variation of particle size of the synthesized nanomaterials. It is clear from the M-H curves that increase in Ce3+contents, paramagnetic behavioralso increases due to the paramagnetic nature of Ce3+ ions [27]. The value of saturation magnetization Ms is lower than the previous quoted values for pure MnZnCd Fe2O4 ferrites. This low value of coecivity was further decreased with increasing concentration of Ce3+ ions. This change may be attributed to the paramagnetic nature of Cerium metal ions and their magnetic moments.
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To study the effect of nanosized domain on magnetic properties, the values of squareness ratio (Mr/Ms) from the MH curves were calculated. The prepared nanoferrites have squrance ratio below 0.5 and lies in the range 0.012-0.044 which shows the single domain behaviour of prepared nanoferrites [28]. The magnetic moment nB per formula unit in Bohr magnetron andmagnetocrystalline anisotropy constant was calculated as K1=MsHc/ 2
(4)
nB (µB) = MsM / 5585
(5)
Where Hc is the Coercivity, M is molecular weight of prepared materials, Ms is the saturation magnetization and µo is the permeability of free space. Table 3 shows that calculated anisotropy values lies in the range 23.27- 141.84 J/m3. These high values of anisotropy constant predict that the anisotropy contribution may not be uniaxial [29-31]. The calculated values of magnetic moments are proportional to saturation magnetization and increases linearly with Ce3+ concentration. Particle size (D), saturation magnetization (Ms) and initial permeability (µi) is interlinked by the following relation[32]. µi = Ms2 D/ K1
(6)
Here k1 is the anisotropy constant. Relation between Ce3+ concentration and initial permeability could be observed in table 3. Linear relationship between µi and grain size was reported previously by Reddy et al [33].
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4. Conclusion In this research paper, we have synthesized Ce3+ substituted Mn-Zn-Cd nanoferrites by coprecipitation method and investigated the influence of Ce3+ ions substitution on the structural, electrical and magnetic properties of grown samples. XRD results showed that the synthesized nanoferrites belongs to fd3m space group.The particle size of these synthesized ferrites lies in the nano regime and found to be decreased by increasing the substitution of Ce3+ ions. FTIR spectra has confirmed the spinel structure of synthesized nanoferrites. Electrical resistivity of these nanoparticles increases with increasing Ce3+ concentration. M-H curves clearly showed the paramagnetic nature and single domain behavior of synthesized samples. All observed properties suggested that these nanoparticles are special candidates for high frequency devices and magnetic recording media. References [1] M. S. Hasan, M. I. Arshad, A. Ali, K. Mahmood, N. Amin, S. S. Ali, M. Saleem, Mg and La co-doped ZnNi spinel ferrites for low resistive applications, Materials Research Express. 6 (2018) 016302. [2] M. Arshad, N. Amin, M. Islam, A. Ali, K. Mahmood, M. Nabi, G. Mustafa, Effects of srsubstitution on the microstructure and magnetic behavior of m-type hexagonal ferrites synthesis by co-precipitation method, Journal of ovonic research. 13 (2017) 203-210. [3] S. Ikram, M. I. Arshad, K. Mahmood, A. Ali, N. Amin, N. Ali, Structural, magnetic and dielectric study of La3+ substituted Cu0.8Cd0.2Fe2O4 ferrite nanoparticles synthesized by the coprecipitation method, Journal of Alloys and Compounds. 769 (2018) 1019-1025.
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[4] I. Ahmad, M. Ahmad, I. Ali, M. Kanwal, M. S. Awan, G. Mustafa, M. Ahmad, Effects of Gd-substitutions on the microstructure, electrical and electromagnetic behavior of M-type hexagonal ferrites, Journal of Electronic Materials. 44 (2017) 2221-2229. [5] M. S. Hasan, M. I. Arshad, A. Ali, K. Mahmood, N. Amin, S. S. Ali, M. Saleem, Mg and La co-doped ZnNi spinel ferrites for low resistive applications, Materials Research Express. 6 (2018) 016302. [6] G. Mustafa, M. U. Islam, W. Zhang, Y. Jamil, A. W. Anwar, M. Hussain, M. Ahmad, Investigation of structural and magnetic properties of Ce3+-substituted nanosized Co–Cr ferrites for a variety of applications, Journal of Alloys and Compounds. 618 (2015) 428-436. [7] S. Ikram, J. Jacob, M. I. Arshad, K. Mahmood, A. Ali, N. Sabir, S. Hussain, Tailoring the Structural, Magnetic and Dielectric properties of Ni-Zn-CdFe2O4 spinel ferrites by the substitution of Lanthanum ions, Ceramics International. 45 (2019) 3563-3569. [8] R. Gimenes, M. D. Baldissera, M. R. A. Da Silva, C. A. Da Silveira, D. A. W. Soares, L. A. Perazolli, M. A. Zaghete, Structural and magnetic characterization of MnxZn1−xFe2O4 (x= 0.2; 0.35; 0.65; 0.8; 1.0) ferrites obtained by the citrate precursor method, Ceramics international. 38 (2012) 741-746. [9] V. J. Angadi, B. Rudraswamy, K. Sadhana, S. R. Murthy, K. Praveena, Effect of Sm3+– Gd3+ on structural, electrical and magnetic properties of Mn–Zn ferrites synthesized via combustion route, Journal of Alloys and Compounds. 656 (2016) 5-12.
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[10] N. Amin, M. I. Arshad, M. U. Islam, A. Ali, K. Mahmood, G. Murtaza, G. Mustafa, Role of y3+ ions on the structural and dielectric properties of Ni-Zn-Cr ferrites synthesized by coprecipitation method, Digest Journal of Nanomaterials and Biostructures. 11 (2016) 579-590. [11] M. A. Khan, M. J. ur Rehman, K. Mahmood, I. Ali, M. N. Akhtar, G. Murtaza, I. Shakir, M. F. Warsi, Impacts of Tb substitution at cobalt site on structural, morphological and magnetic properties of cobalt ferrites synthesized via double sintering method, Ceramics International. 41 (2015) 2286-2293. [12] M. Y. Lodhi, K. Mahmood, A. Mahmood, H. Malik, M. F. Warsi, I. Shakir, M. A. Khan, New Mg0.5CoxZn0.5−xFe2O4 nano-ferrites: structural elucidation and electromagnetic behavior evaluation, Current Applied Physics. 14 (2014) 716-720. [13] H. Malik, A. Mahmood, K. Mahmood, M. Y. Lodhi, M. F. Warsi, I. Shakir, M. A. Khan, Influence of cobalt substitution on the magnetic properties of zinc nanocrystals synthesized via micro-emulsion route, Ceramics International. 40 (2014) 9439-9444. [14] G. Mustafa, M. U. Islam, W. Zhang, A. W. Anwar, Y. Jamil, G. Murtaza, M. Ahmad, Influence of the divalent and trivalent ions substitution on the structural and magnetic properties of Mg0.5−xCdxCo0.5Cr0.04TbyFe1.96− yO4 ferrites prepared by sol–gel method, Journal of Magnetism and Magnetic Materials. 387 (2015) 147-154. [15] D.Ravinder, Far-infrared spectral studies of mixed Lithium-Zinc ferrites, Mater. Letter. 1016 (1999) 205-208. [16] B. Baruwati, K. M. Reddy, S. V. Manorama, R. K. Singh, O. Parkash, Tailored conductivity behavior in nanocrystalline nickel ferrite, Applied physics letters. 85 (2004) 2833-2835.
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[17] I. H. Gul, A. Maqsood, Structural, magnetic and electrical properties of cobalt ferrites prepared by the sol–gel route, Journal of Alloys and Compounds. 465 (2008) 227-231. [18] I. H. Gul, W. Ahmed, A. Maqsood, Electrical and magnetic characterization of nanocrystalline Ni–Zn ferrite synthesis by co-precipitation route, Journal of Magnetism and Magnetic Materials. 320 (2008) 270-275. [19] E. Rezlescu, L. Sachelarie, P. D. Popa, N. Rezlescu, Effect of substitution of divalent ions on the electrical and magnetic properties of Ni-Zn-Me ferrites, IEEE transactions on magnetics. 36 (2000) 3962-3967. [20] R. Zahra, K. Mahmood, A. Ali, U. Rehman, N. Amin, M. I. Arshad, M. H. Mahmood, Growth of Zn2GeO4 thin film by thermal evaporation on ITO substrate for thermoelectric power generation applications, Ceramics International. 45 (2019) 312-316. [21] A. A. Kadam, S. S. Shinde, S. P. Yadav, P. S. Patil, K. Y. Rajpure, Structural, morphological, electrical and magnetic properties of Dy doped Ni–Co substitutional spinel ferrite, Journal of Magnetism and Magnetic materials. 329 (2013) 59-64. [22] R. Mohamed, M. M. Rashad, F. A. Haraz and W. Sigmund, Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method, J. mag. magn. Mater. 322 (2010) 2058-2064. [23] Arslan Ashfaq, J. Jacob, N. Bano, A. Ali, W. Ahmad, K. Mahmood, M I Arsha, S. Ikram, U. Rehman, S. Hussain, Tailoring the thermoelectric properties of sol-gel grown CZTS/ITO thin films by controlling the secondary phases, Physica B. 558 (2019) 86. [24] S. S. Abbas, I. H. Gul, S. Ameer, M. Anees, Ce-Substituted Co0.5Ni0.5Fe2O4: Structural, Morpphological, Electrical, and Dielectric Properties, Electron matter. 100 (2015) 100-108.
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[25] E. Pervaiz, I. H. Gul, High frequency AC response, DC resistivity and magnetic studies of holmium substituted Ni-ferrite: a novel electromagnetic material, Journal of magnetism and magnetic materials. 349 (2014) 27-34. [26] Z. Peng, X. Fu, H. Ge, Z. Fu, C. Wang, L. Qi, H. Miao, Effect of Pr3+ doping on magnetic and dielectric properties of Ni–Zn ferrites by one-step synthesis, J. Mag. Magn. Mater. 323, (2011) 2513-2518. [27] J. H. Nam, H. H. Jung, J. Y. Shin, J. H. Oh, The effect of Cu substitution on the electrical and magnetic properties of NiZn ferrites. IEEE Transactions on Magnetics, 31 (1995) 39853987. [28] C. B. Kolekar, P. N. Kamble, A. S. Vaingankar, Structural and dc electrical resistivity study of Gd3+-substituted Cu-Cd mixed ferrites, Journal of magnetism and magnetic materials. 138 (1994) 211-215. [29] M. Sugimoto, The past, present, and future of ferrites, Journal of the American Ceramic Society. 82 (1999) 269-280. [30] C. Venkataraju, G. Sathishkumar, K. Sivakumar, Effect of Cd on the structural, magnetic and electrical properties of nanostructured Mn–Zn ferrite, Journal of Magnetism and Magnetic Materials. 323 (2011) 1817-1822. [31] W. A. Wooster, Physical properties and atomic arrangements in crystals, Reports on Progress in Physics. 16 (1953) 62. [32] B. Baruwati, K. M. Reddy, S. V. Manorama, R. K. Singh, O. Parkash, Tailored conductivity behavior in nanocrystalline nickel ferrite, Applied physics letters. 85 (2004) 2833-2835.
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[33] C. G. Reddy, S. V. Manorama, V. J. Rao, Semiconducting gas sensor for chlorine based on inverse spinel nickel ferrite, Sensors and Actuators B: Chemical. 55 (1999) 90-95. List of Figures and Tables: Figure 1:- XRD diffractograms of Mn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites with different concentration of Ce3+ ions . Figure 2:- Room temperature FTIR spectra of Mn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites (where y= 0.0 - 0.7). Figure 3:- Plot between resistivity and temperature of synthesized Mn0.43Zn0.5 Cd.07Cey Fe2-y O4 nanoferrites (where y= 0.0 - 0.7). Figure 4:- Plot between lnρ and 1000/T of synthesizedMn0.43Zn0.5Cd.07CeyFe2-yO4 nanoferrites (where y= 0.0 - 0.7). Figure 5:- The MH- loop for Mn0.43Zn0.5 Cd.07Cey Fe2-y O4(y= 0.1, 0.3, 0.5) nanoferrites Table 1:- Effect of Ce3+ substitution on Crystallite size (D), Lattice constant (ɑ) and Cell volume (Vcell),
packing
factor,
x-ray
density,
bulk
density
and
porosity
of
synthesized
Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites. Table 2:- Effect of Ce3+ substitution on high frequency band (ʋ1), low frequency band (ʋ2), Rt, Ro, and force constants Kt and Ko ofsynthesized Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites. Table 3:- Effect of Ce3+ substitution on saturation magnetization (Ms), remanence (Mr), coercivity (Hc), squarance ratio, anisotropy constant K1 and bohar magneton nB(µB) ofsynthesized Mn0.43Zn0.5Cd.07CeyFe2-yO4(y = 0.0-0.7) nanoferrites.
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Figure 1
y =0.7
intensity (a.u)
y =0.5
y =0.3 y =0.2
y=0.1
y = 0.0 20
25
30
35
40
2 Theta (degree)
45
50
55
60
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Figure 2
Transmittence (%)
y=0.7
y=0.5 y=0.3 y=0.1 y=0.0
800
750
700
650
600
Wave number cm-1
550
500
450
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Fig. 3
10
6x10
10
Resistivity (Ohm-Cm)
5x10
y = .7
10
4x10
y = .5
10
y = .4
10
y = .3
3x10
2x10
y= .2
10
1x10
y = .1 250
300
350
400
450
500
Temperature (K)
550
600
650
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Fig. 4
60
y= 0.7 y= 0.5 50
ln cm)
y = 0.4 y = 0.3
40
y = 0.2 30
y = 0.1
20
1.5
2.0
2.5
3.0 -1
1000/T (K )
3.5
4.0
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Fig. 5
0.04
y= .1 y= .3 y= .5
Magnatization (emu/g)
0.03 0.02 0.01 0.00 -0.01 -0.02 -0.03 -0.04
-30000
-20000
-10000
0
10000
Magnetic Field (Oe)
20000
30000
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Table 1 y
0.0
Lattice Constant ‘a’
Cell volume
(Ǻ)
(Ǻ3)
‘a3’
Particle size ‘t’
Packing Factor
x-ray density
Bulk density
(nm)
P
ρx (g/cm3)
ρm (g/cm3)
Porosity %
8.437269
600.6281
43.1274186
169.5305277
5.304532
3.84741
27.46937
8.437269
600.6281
42.685562
167.7936235
5.490986
3.94284
28.1943
8.43032
599.1454
38.26144
150.5267164
5.69149
4.054414
28.76358
8.425694
598.1596
41.7944036
164.5162419
5.887871
4.173092
29.12393
8.448877
603.1106
46.5056932
182.5590935
6.210909
4.912555
20.90441
8.421074
597.1761
41.3816624
162.9809366
6.647472
5.10624
23.18523
ʋ1
ʋ2
Rt
Ro
Kt
Ko
(cm-1)
(cm-1)
(Ǻ)
(Ǻ)
(erg/cm3)
(erg/cm3)
0.0
543.18
452.28
0.476669
0.759317
170032.4
287930.2
0.1
544.04
456.74
0.476669
0.759317
174098.3
292398.7
0.3
542.66
451.19
0.474163
0.756424
171134.9
290219.1
0.5
541.98
450.66
0.479182
0.762219
171839.7
291391.6
0.7
541.18
449.76
0.473162
0.755268
172143.4
292058.9
0.1 0.2 0.3 0.5 0.7
Table 2 y
Journal Pre-proof
Table 3 Y
Saturaton magnetizatio n Ms (emu/g)
Remanence Mr (emu/g)
Coercivit y Hc (Oe)
Mr / Ms
Anisotropy constant K1 (J/m3)
Initial permeability µi
nB(µB)
0.1
22.98
1.02
12.345
0.04438
141.8441
158.5982989
1.0214
0.3
24.62
0.34
4.07
0.01381
50.1017
504.4982801
1.1686
0.5
18.22
0.22
2.555
0.01207
23.27605
663.1937378
0.9198
Journal Pre-proof
Journal Pre-proof
Declaration of interests ☐The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
I confirmed above both statements