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Structural, optical and magnetic properties of Tb3+ substituted Co nanoferrites prepared via sonochemical approach
Accepted Manuscript Structural, optical and magnetic properties of Tb prepared via sonochemical approach
3+
substituted Co nanoferrites
A. Sadaqat, M. Almessiere, Y. Slimani, S. Guner, M. Sertkol, H. Albetran, A. Baykal, Sagar E. Shirsath, B. Ozcelik, I. Ercan PII:
S0272-8842(19)32105-4
DOI:
https://doi.org/10.1016/j.ceramint.2019.07.280
Reference:
CERI 22395
To appear in:
Ceramics International
Received Date: 23 May 2019 Revised Date:
23 July 2019
Accepted Date: 24 July 2019
Please cite this article as: A. Sadaqat, M. Almessiere, Y. Slimani, S. Guner, M. Sertkol, H. Albetran, 3+ A. Baykal, S.E. Shirsath, B. Ozcelik, I. Ercan, Structural, optical and magnetic properties of Tb substituted Co nanoferrites prepared via sonochemical approach, Ceramics International (2019), doi: https://doi.org/10.1016/j.ceramint.2019.07.280. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Structural, optical and magnetic properties of Tb3+ substituted Co nanoferrites prepared via sonochemical approach
Baykalg, Sagar E. Shirsathh, B. Ozceliki and I. Ercanb
a
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A. Sadaqata1, M. Almessiereb,c, Y. Slimanib, S. Gunerd, M. Sertkole, H. Albetranf, A.
Department of Mechanical and Energy Engineering, College of Engineering, Imam
Department of Biophysics, Institute for Research and Medical Consultations (IRMC), Imam
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b
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Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia.
Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia. c
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O.
Box 1982, 31441, Dammam, Saudi Arabia. d
Institute of Inorganic Chemistry, RWTH Aachen University, D-52074 Aachen, Germany.
e
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Deanship of Preparatory Year Building 450, Imam Abdulrahman Bin Faisal University, P.O.
Box 1982, 31441, Dammam, Saudi Arabia. f
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Department of Basic Sciences, College of Education, Imam Abdulrahman Bin Faisal
University, 31451, Dammam, Saudi Arabia. g
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Department of Nanomedicine Research, Institute for Research and Medical Consultations
(IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia. h
School of Materials Science and Engineering, University of New South Wales, Kensington,
Sydney, NSW 2052, Australia. i
Department of Physics, Faculty of Science and Letters, Cukurova University, 01330 Balcali,
Adana, Turkey. 1
Corresponding author`s email:[email protected] (Ali Sadaqat). Tel: + 9 66 54 819 862366
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Abstract This paper emphasizes the structure, morphology, optical, and magnetic properties of
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sonochemically prepared terbium-substituted cobalt ferrite nanoparticles, CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10). The formation of cubic spinel nanosized ferrite structure was confirmed by X-ray diffraction (XRD), Field-emission scanning electron microscopy (FE-SEM), and Fourier-
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transform infrared (FT-IR) spectroscopy. The crystallites sizes were found in the range of 11 - 14 nm. Ultraviolet-visible percentage diffuse reflectance investigations were performed on
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pristine and Tb3+-doped cobalt spinel ferrite CoFe2O4 nanoparticles. The direct energy band gap (Eg) values were determined by applying the Kubelka–Munk theory and Tauc plots were found to be in a narrow band range of 1.37 to 1.44 eV. Analyses of magnetization versus the magnetic field (M(H)) were performed. The magnetic parameters, including the saturation ), remanence
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magnetization (Ms), squareness ratio (SQR = Mr/Ms), magnetic moment (
(Mr), and coercivity (Hc) were evaluated. The M(H) curves exhibited a soft ferrimagnetic nature. It was demonstrated that the Tb3+ substitutions strongly influenced the magnetization
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data. Indeed, the Ms, Mr, Hc, and
values decreased with increasing Tb3+ substitution.
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Keywords: Spinel ferrite; Structure; Cation distribution; Microstructure; Optical properties; Magnetic properties.
1. Introduction Spinel ferrite nanoparticles (MFe2O4) play a very important role in industrial and scientific applications [1–2], such as magneto-strictive sensors, actuators, drug delivery, gas sensors, solar cells, memory devices, transducers, hyperthermia, supercapacitors, spintronic devices,
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ACCEPTED MANUSCRIPT and microwaves [3–7]. Cobalt nanospinel ferrites, such as CoFe2O4, have the most favorable ferrimagnetic materials, exhibiting exceptional properties, and are based on the grains size and cation distributions at the tetrahedral 64 A-sites and octahedral 32 B-sites in the spinel ferrite structure [7–9]. Cobalt spinel ferrite is used extensively owing to certain beneficial
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features, including high magneto-crystalline anisotropy, chemical stability, coercivity (Hc), saturation magnetization (Ms), and high Curie temperature [10–11]. Many researchers have demonstrated the chemical, dielectric, physical, optical, and magnetic characteristics based on
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cation substitution and synthesized materials. Numerous techniques are applied to synthesize spinel ferrite nanoparticles, such as the co-precipitation method, sol-gel auto-combustion
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technique, solvothermal method, micro-emulsion method, and hydrothermal method [12–14]. Rare earth (RE) ions play a very important role in changing the ferrite structure, owing to their large radius and stable valency. In recent years, the physical properties have been improved by substituting RE ions into the spinel ferrite nanostructure [15–16]. Nanospinel
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ferrites are very helpful in controlling the electromagnetic pollution, with their significant resistivities and magnetic losses operating as electromagnetic wave-absorbing materials [17]. RE substitution has an excellent effect on controlling the electromagnetic and
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crystallographic properties in the spinel ferrite structure. RE oxides are used as electrical
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insulators owing to their excellent resistivity (106 Ω.cm) at room temperature [18–20]. The lanthanides series Pr, Pm, Dy, Y, Nd, Sm, Ce, Er, and La play a significant role in substitution of the ferrites structure [21]. The ionic radii and magnetic parameters can be controlled with the addition of RE in spinel ferrites [22]. RE ions have a significant effect in modifying the electromagnetic traits of ferrites, which is the reason for the strong spin-orbit couplings of unpaired 4f electrons. The electromagnetic properties exhibit a strong influence and interaction between RE and Fe (3d–4f coupling) in nanoferrites [23, 24]. The sol-gel auto-combustion process was employed to produce CoxZnxGdxFe2−xO4 nanoparticles, and the
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ACCEPTED MANUSCRIPT electrical and elastic properties by substitution of Gd3+ ions in cobalt-zinc ferrite were studied [25]. Pachpinde et al. [26] synthesized PrxCoFe2−xO4 nanoparticles in a sol-gel autocombustion method and noted that the saturation magnetization was improved with the substitution of Pr3+ in cobalt spinel ferrites. Singh et al. [27] observed that the coercive field
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(Hc) and saturation magnetization (Ms) values were decreased with an increase of the RE (Pr, Sm, and La) contents in Ni-Zn nanoferrites. Materials of NixZnxFe1.95RxO4 were prepared by the citrate precursor process and also annealed at 450 °C. Finally, the process was noted as
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highly valuable for recording and microwave applications. Almessiere et al. [28] prepared a CoTmxFe2−xO4 (0.0 ≤ x ≤ 0.08) nanocomposite using the sonochemical approach. In this
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study, it was observed that the Hc and Ms values were improved with the doping of Tm3+ into Co-spinel ferrites. Abdellahi et al. [29] reported that the permeability decreased and resistivity increased with the addition of Tb3+-doped nanocrystalline NiCuZn nanoferrite particles.
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To the best of our knowledge, the series of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles were synthesized via sonochemical method for the first time in this study. The impact of Tb3+ ion substitution on the microstructure, morphology, spectral, optical and
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magnetic properties of spinel CoFe2O4 ferrites was deeply investigated.
2. Experiment
The sonochemical method was employed to fabricate CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O), iron (III) nitrate nonahydrate ((Fe(NO3)3·9H2O), and terbium oxide (Tb4O7) were utilized as the starting materials. A specific amount of salt nitrite was dissolved in deionized (DI) water, which formed the first solution. The second solution was Tb4O7 dissolved in 10 ml of concentrated HCl at 180 °C. The two solutions were mixed together, and the pH was adjusted to 11 by using 2 M of
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ACCEPTED MANUSCRIPT NaOH solution. The resulting solution was exposed to ultrasonic irradiation for 60 min. The powder was washed frequently with DI water. The magnetic powder was detached from the mixture by an outer magnet, and then dried at 60 °C for 12 h. The structure was analyzed using the Rigaku Benchtop Miniflex X-ray diffraction (XRD)
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with CuKα radiation. A Field-emission scanning electron microscope (FE-SEM; FEI Titan ST) coupled with an energy dispersive X-rays (EDX) spectrometer system was utilized for the surface morphology and chemical compositions. The Fourier-transform infrared (FT-IR)
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spectra were restarted using a wavelength range from 4000 to 400 cm−1. The magnetic properties were determined using a superconducting quantum interference device (SQUID)
3. Results and discussion 3.1. Structural
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from Quantum Design coupled with a vibrating sample magnetometer (VSM) head.
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The XRD powder patterns of the CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles are illustrated in Figure 1. All X-ray peaks correspond to the spinel cubic structure, which refers to the Fd3m space group symmetry. Furthermore, there is no indication of any second phase, which
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proves that all specimens were pure and of a single spinel structure. The XRD peak at (311)
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was shifted in the direction of lower diffraction angles with the addition of the Tb content. This shifting was caused by the disordering of the spinel lattice. Software (Match3!) was used to evaluate the crystallite size and lattice parameters (Table 1). It was demonstrated that the lattice parameters were reduced from x = 0.00 to x = 0.04 and the remaining ratios were increased. This diversity could be attributed to the larger ionic radii of Tb3+ (1.06 Å) compared to Co2+ (0.745 Å) and Fe3+ (0.645 Å). The lattice was broadened as a consequence of the distortion in the lattice [30,31]. The crystallite size of all compositions was almost constant, between 11 and 14 nm (Table 1), owing to the stability of the full width at half
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ACCEPTED MANUSCRIPT maximum. İt has been proven that a very small amount of Tb incorporated into the spinel lattice can also alter the magnetic properties. This type of change has been described for cobalt RE spinel ferrite. The cation distribution is presented in Table 2, which indicates that
Figure 1.
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3.2. FT-IR
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the preference of Tb3+ ions is Oh sites [32].
Figure 2 displayed FT-IR spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) NPs. All compositions
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presented FT-IR absorption bands at 579 and 407 cm-1 (the respective vibrational modes of Me-O (metal-oxide), similar to the vibration bands of tetrahedral and octahedral sites individually [33-35]. It has been notice that the substitution of the Tb3+ ion into the cobalt ferrite has to some extent shifted peaks in the direction of the higher frequency side. The
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shifting of peaks has been indicate the micro-strain in the cobalt ferrite lattices reason by the larger sized Tb3+ ion substitution and changing in the distance of iron oxygen bond. Furthermore, the intensity of the peaks (574 cm−1) vibrational mode is slowly increased with
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increasing Tb3+ substitution [36].
Figure 2.
3.3. Morphology
FE-SEM images of the different nanoparticles are presented in Figure 3. The micrographs exhibited a high degree of aggregation of the spherical nanoparticles because of the high magnetization of the spinel ferrite [38]. The particle size was found to be less than 20 nm for all compositions, with no substantial modification when increasing the Tb substitution, as illustrated in Figure 1, which was confirmed by the XRD analysis. The EDX and elemental
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ACCEPTED MANUSCRIPT mapping verified the presence of elements consisting of Tb substituted Co-nanoferrites (Figure 4).
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Figure 3.
Figure 4.
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3.4. Optical
Percent diffuse reflectance (DR %) measurements were performed on the CoTbxFe2-xO4 (x =
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0.00 to 0.10) nanospinel ferrites using an ultraviolet-visible (UV-Vis) spectrophotometer in a sweep range of 200 to 800 nm. The recorded spectra are displayed in Figure 5. The DR % magnitudes exhibited an intensity band of 12% to 15% in the near UV (200 to 380 nm) and visible (380 to 740 nm) regions of electromagnetic radiation. Above 740 nm, the reflectance
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intensities increased slightly in the remaining sweep range of the spectrophotometer. The optical energy band gap (Eg) values were calculated as follows [37-41]:
where
=
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=
is the Kubelka–Munk function,
(1) provides the DR ratio between
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the measured and reference samples, A is a constant of proportionality, hυ is the incident photon energy, and the exponent n is related to the types of electronic transitions. Exponent values of n = 1/2 and n = 2 correspond to direct and indirect allowed transitions, respectively. Therefore, the direct Eg values belonging to each sample were determined by extrapolating the linear part of the [
ℎυ]2 versus photon energy plots for [
ℎυ] = 0 eV. These
plots are also known as Tauc plots, and the extrapolated Eg values are presented in Figure 6 for all the CoTbxFe2-xO4 (x = 0.00 to 0.10) nanospinel ferrites. All of the Tauc plots had yaxis exponents equal to 2 and this case assigned the direct allowed transitions for the undoped 7
ACCEPTED MANUSCRIPT and Tb3+ doped nanoparticles. The estimated band gap of pristine CoFe2O4 is 1.37 eV. Comparing this value with the estimated energy band gaps of the doped nanospinel ferrites, it can easily be observed that the Tb3+ ions caused slight increments until the maximum band gap of 1.44 eV belonging to the CoTb0.10Fe1.90O4 nanospinel ferrites. The order of the Eg
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values reveals the semiconducting nature of all the samples. In the literature, direct or indirect Eg data are reported for pristine and doped cobalt ferrites with different elements, such as Zn, Ni, Y, and Nb [42-50]. The reported Eg magnitudes for direct or indirect allowed transitions
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are within a wide range between 0.48 and 4.3 eV. In the literature, Tatarchuk et al. and
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Quinonez et al. reported the closest data to our direct optical Eg values [42, 45].
Figure 5.
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3.5. Magnetization
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Figure 6.
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Figure 7 illustrates the magnetization as a function of applied magnetic field, M(H), hysteresis loops for various CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles. It is obvious that the Tb3+ substitutions in the Fe3+ sites played a significant role in developing the magnetic properties of the CoFe2O4. The Stoner–Wohlfarth (S–W) methodology was employed to deduce the saturation magnetization (Ms) values [51-55]. The synthesized nanoparticles exhibited saturation magnetization (Ms), remanant magnetization (Mr), and coercive field (Hc) magnitudes in the ranges of 9.1 to 26.7 emu/g, 2.33 to 4.22 emu/g, and 199.4 to 317.6
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Figure 7.
The impact of the Tb3+ substitutions on the Ms, Mr, and Hc of the studied CoTbxFe2xO4
nanoparticles were evaluated. The pristine CoFe2O4 (x = 0.00) sample exhibited Ms
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values equal to 26.7 emu/g. The obtained magnitude was lower than that of the bulk CoFe2O4 (Ms ~ 80 emu/g) [56,57], which was primarily attributed to the presence of tinier nano-
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crystallites in the sample. In fact, this would lead to spins disordering through a large surfaceto-volume ratio [58], thereby lowering the Ms. The occurrences of canted spins owing to competitive antiferromagnetic interactions and the resultant disordered distribution of cations on the sample surface could be responsible for the reduced Ms value [59,60]. The Ms and Mr
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values for the various proposed compositions exhibited a diminishing trend with the increase in the Eu3+ concentration, wherein the Ms and Mr were lowest for the sample with x = 0.10. Both the Ms and Mr followed the same tendency with an increasing Tb3+ doping content [59].
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Various studies have suggested that the change in the magnetic traits of doped spinel
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nanoferrites are governed by the presence of strains, variations in grains sizes and their distributions, strength of the super-exchange interaction, and variations in
. The reduction
in the Ms values with the reduction in the grain size has been described in several investigations [61,62]. Here, the reduction in the Ms and Mr values with the increase in Tb3+ content agreed with the XRD findings, which demonstrated a reduction in the crystallite sizes, and therefore a reduction in the magnetizations. Furthermore, the substitution of Fe3+ with ionic radii of 0.645 Å by Tb3+ ions with larger ionic radii (1.06 Å) could create local strains and disorder in the ferrite system, which would alter the electronic states and magnetic
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ACCEPTED MANUSCRIPT traits. Moreover, it has been reported that the relation between magnetic moment (
) and
saturation magnetization (Ms) can be expressed as [58,53]: !" # $% & ' ( . ))*)
=
for the synthesized
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Figure 8(c) displays the Tb3+ content dependent variation in the nanoparticles. Generally, the decrease in
is resulted from the weakening of the super-
exchange interactions among various sites. In the present study, the x = 0.00 composition decreases with increasing Tb3+ substitution
and Ms.
content. The observed reduction in the
values is attributed to the weakening of the super-
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exhibited maximum values of
shows similar lowering
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exchange coupling among various lattice sites. The evolution of
tendency to that of Ms and Mr when the Tb3+ content increases. The squareness ratio (SQR) values were also determined and are presented in Figure 8(e). The SQR values for nanoferrites with cubic and uniaxial anisotropy are generally known to be close to 0.83 and 0.50, respectively [58,63]. If the SQR is equal to or above 0.5, nanoparticles are known to
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exist in multiple magnetic domain structures [58,63]. However, if the SQR is below 0.5, the nanoparticles are known to occur in a single magnetic domain (SMD) structures [55, 60]. For
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the various synthesized nanoparticles, the SQR values obtained suggest a uniaxially anisotropic SMD character. It is worth noting that SQR values below than 0.5 signify the
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presence of strong surface spin disordering [58,63].
Figure 8.
4. Conclusion
The influence of Tb3+ substitution on the structural, morphology, optical and magnetic properties of cobalt ferrite nanoparticles, CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10), synthesized by the sonochemical approach was examined in detail. The incorporated Tb3+ in the spinel structure was verified by XRD. The DXRD values were found to be in the range of 11 to 14 nm. FE10
ACCEPTED MANUSCRIPT SEM investigations revealed a spherical structure and particles size that correspond with the XRD analysis. The direct Eg estimated from DR % data are found in the range of 1.37 to 1.44 eV, revealing the semiconductor characteristics of all nanoparticles. The Eg values increased slightly owing to the Tb3+ ion doping process. M(H) analyses showed soft ferrimagnetic
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behavior for various nanoparticles. The values of magnetic parameters, Ms, Mr, and
, for
the synthesized nanoparticles were decreased with the increase in Tb3+ substitution contents. Such observations could be attributed to the presence of strains, weakening of the super-
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exchange interaction, reduction in crystallites size, surface spin disorder, and reduction in
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magnetic moment.
Acknowledgements
This study was supported by the Deanship for Scientific Research (project applications 2017576-IRMC and 2018-209-IRMC) of Imam Abdulrahman Bin Faisal University (Saudi
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References
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Arabia).
[1] S. Karimunnesa, A.K.M.A. Ullah, M.R. Hasan, F.S. Shanta, R. Islam, M.N.I. Khan,
AC C
Effect of holmium substitution on the structural, magnetic and transport properties of CoFe2-xHoxO4 ferrites, J. Magn. Magn. Mater. 457 (2018) 57–63. [2] S.K. Gore, R.S. Mane, M. Naushad, S.S. Jadhav, Influence of Bi3+-doping on the magnetic and Mössbauer properties of spinel cobalt ferrite, (2015) 6384–6390. [3] A.A. Khan, U. Hira, Z. Iqbal, M. Usman, F. Sher, Structural, magnetic and magnetocaloric properties of CoFe2−xMoxO4 (0.0≤x≤0.3) ferrites, Ceram. Int. 43 (2017) 7088–7093.
11
ACCEPTED MANUSCRIPT [4] M.S. Hossain, B. Alam, M. Shahjahan, Synthesis, structural investigation, dielectric and magnetic properties of Zn2+-doped cobalt ferrite by the sol – gel technique, J. Adv. Dielectrics 8 (2018) 2–7. [5] M. Gharibshahian, M.S. Nourbakhsh, O. Mirzaee, Evaluation of the superparamagnetic
RI PT
and biological properties of microwave assisted synthesized Zn & Cd doped CoFe2O4 nanoparticles via Pechini sol--gel method, J. Sol-Gel Sci. Technol. 85 (2018) 684–692. [6] M. Ansari, A. Bigham, S.A. Hassanzadeh-Tabrizib, H. Abbastabar Ahangar, Synthesis
system, J. Magn. Magn. Mater. 439 (2017) 67-75.
SC
and characterization of Cu0.3Zn0.5Mg0.2Fe2O4 nanoparticlesas a magnetic drug delivery
M AN U
[7] M.K. Zate, V. V Jadhav, S.K. Gore, J.H. Shendkar, S.U. Ekar, A. Al-Osta, M. Naushad, R.S. Mane, Structural, morphological and electrochemical supercapacitive properties of sprayed manganese ferrite thin film electrode, J. Anal. Appl. Pyrolysis. 122 (2016) 224– 229.
TE D
[8] R.H. Kodama, A.E. Berkowitz, E.J. McNiff, S. Foner, Surface spin disorder in ferrite nanoparticles, J. Appl. Phys. 81 (1998) 5552. [9] M.A. Almessiere, Y. Slimani, A.D. Korkmaz, N. Taskhandi, M. Sertkol, A. Baykal, Sagar
EP
E. Shirsath, İ. Ercan, B. Ozçelik, Sonochemical synthesis of Eu3+ substituted CoFe2O4
AC C
nanoparticles and their structural, optical and magnetic properties, Ultrasonics Sonochemistry 58 (2019) 104621. [10] N. Kasapoğlu, A. Baykal, Y. Köseoğlu, M.S. Toprak, Microwave-assisted Combustion Synthesis of CoFe2O4 with Urea and its magnetic Characterization, Scriptia Materialia, 57 (2007) 441-444. [11] D.L. Zhao, Fabrication and microwave absorbing properties of Ni–Zn nanospinel ferrites, J. Alloys Compd. 480 (2009) 634–638.
12
ACCEPTED MANUSCRIPT [12] Y. Slimani, M.A. Almessiere, M. Nawaz, A. Baykal, S.Akhtar, I. Ercan, I. Belenli, Effect of bimetallic (Ca, Mg) substitution on magneto-optical properties of NiFe2O4 nanoparticles, Cer Int 45 (2019) 6021-6029. [13] F. Li, J. Liu, D.G. Evans, X. Duan, Stoichiometric Synthesis of Pure MFe2O4 (M = Mg,
RI PT
Co, and Ni) Nanospinel ferrites from Tailored Layered Double Hydroxide (Hydrotalcite-Like) Precursors, Chem. Mater. 16 (2004) 1597–1602.
[14] M.M.L. Sonia, S. Anand, V.M. Vinosel, M.A. Janifer, S. Pauline, A. Manikandan, Effect
SC
of lattice strain on structure, morphology and magneto-dielectric properties of spinel
Mater. 466 (2018) 238–251.
M AN U
NiGdxFe2−xO4 ferrite nano-crystallites synthesized by sol-gel route, J. Magn. Magn.
[15] M. Akhtar, M. Khan, Effect of rare earth doping on the structuraland magnetic features of nanocrystalline nanospinel ferrites prepared via sol gel route, J. Magn. Magn. Mater. 460 (2018) 12111–12111.
TE D
[16] C. Srinivas, Structural and magnetic characterization of co-precipitated NixZn1−xFe2O4 ferrite nanoparticles, J. Magn. Magn. Mater. 407 (2016) 135–141. [17] C. Stergiou, Magnetic, dielectric and microwave absorption properties of rare earth
AC C
629–635.
EP
doped Ni–Co and Ni–Co–Zn nanospinel ferrites, J. Magn. Magn. Mater. 426 (2017)
[18] M. Ajmal, The influence of Ga doping on structural magnetic and dielectric properties of NiCr0.2Fe1.8O4 spinel ferrite, Physica B. Condens. Matter. 526 (2017) 149–154. [19] N. Lwin, M.N.A. Fauzi, S. Sreekantan, R. Othman, Physical and electromagnetic properties of nanosized Gd substituted Mg–Mn ferrites by solution combustion method, Phys. B Condens. Matter. 461 (2015) 134–139. [20] A.A. Sattar, A.H. Wafik, K.M. El-shokrofy, Magnetic Properties of Cu ± Zn Ferrites Doped with Rare Earth Oxides, phys. stat. sol. (a) 563 (1999) 563–570.
13
ACCEPTED MANUSCRIPT [21] K. V Zipare, S.S. Bandgar, G.S. Shahane, Effect of Dy-substitution on structural and magnetic properties of MnZn ferrite nanoparticles, J. Rare Earths. 36 (2018) 86–94. [22] M.H. Abdellatif, Magnetic characterization of rare earth doped spinel ferrite, J. Magn. Magn. Mater. 442 (2017) 445–452.
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[23] M. Hashim, M. Raghasudha, S.S. Meena, J. Shah, S.E. Shirsath, S. Kumar, D. Ravinder, P. Bhatt, Alimuddin, R. Kumar, R.K. Kotnala, Influence of rare earth ion doping (Ce and Dy) on electrical and magnetic properties of cobalt ferrites, J. Magn. Magn. Mater. 449
SC
(2018) 319–327.
[24] G. Dascalu, Structural, electric and magnetic properties of CoFe1.8RE0.2O4 (RE=Dy, Gd,
M AN U
La) bulk materials, J. Magn. Magn. Mater. 333 (2013) 69–74.
[25] R.A. Pawar, S.S. Desai, S.M. Patange, S.S. Jadhav, K.M. Jadhav, Inter-atomic bonding and dielectric polarization in Gd3+ incorporated Co-Zn ferrite nanoparticles, Phys. B Condens. Matter. 510 (2017) 74–79.
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[26] A.M. Pachpinde, Impact of larger rare earth Pr3+ ions on the physical properties of chemically derived PrxCoFe2−xO4 nanoparticles, Chem. Phys. 429 (2014) 20–26. [27] R.K. Singh, Magnetic and dielectric properties of rare earth substituted
EP
Ni0.5Zn0.5Fe1.95R0.05O4 (R = Pr, Sm and La) ferrite nanoparticles, Mater. Sci. Eng. B 210
AC C
(2016) 64–69.
[28] M.A. Almessiere, Y. Slimani, A.D. Korkmaz, S. Guner, M. Sertkol, S.E. Shirsath, A. Baykal, Structural, optical and magnetic properties of Tm3+ substituted cobalt nanospinel ferrites synthesized via sonochemical approach, Ultrason. Sonochem. 54 (2019) 1-10. [29] S.M. Kabbur, S.D. Waghmare, D.Y. Nadargi, S.D. Sartale, R.C. Kambale, U.R. Ghodake, S.S. Suryavanshi, Magnetic interactions and electrical properties of Tb3+ substituted NiCuZn ferrites, J. Magn. Magn. Mater. 473 (2019) 99–108.
14
ACCEPTED MANUSCRIPT [30] S.D. Bhame, P.A. Joy, Magnetoelastic properties of terbium substituted cobalt ferrite, Chem. Phys. Lett. 685 (2017) 465–469. [31] G. Bulai, L. Diamandescu, I. Dumitru, S. Gurlui, M. Feder, O.F. Caltun, Effect of rare earth substitution in cobalt ferrite bulk materials, J. Magn. Magn. Mater. 390 (2015)
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123–131.
[32] V.S. Puli, S. Adireddy, C.V Ramana, Chemical bonding and magnetic properties of gadolinium (Gd) substituted cobalt ferrite, J. Alloys Compd. 644 (2015) 470–475.
SC
[33] B. Labde, M.C. Sable, N. Shamkuwar, Structural and infra-red studies of Ni1+xPbxFe2−2xO4 system, Mater. Lett. 57 (2003) 1651–1655.
M AN U
[34] M.A. Almessiere, Y. Slimani, S. Guner, M. Sertkol, A. Demir Korkmaz, Sagar E. Shirsath, A. Baykal, Sonochemical synthesis and physical properties of Co0.3Ni0.5Mn0.2EuxFe2−xO4 nano-spinel ferrites, Ultrasonics Sonochemistry 58 (2019) 104654.
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[35] A. Baykal, N. Kasapoglu, Y. Koseoglu, M.S. Toprak, H. Bayrakdar, CTAB-assisted hydrothermal synthesis of NiFe2O4 and its magnetic characterization, J. Alloys Compd. 464 (2008) 514–518.
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[36] R. Sharma, S. Bansal, S. Singhal, Augmenting the catalytic activity of CoFe2O4 by
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substituting rare earth cations into the spinel structure, RSC Adv. 6 (2016) 71676– 71691.
[37] J. Tauc, R. Grigorovici, A. Vancu, Optical properties and electronic structure of amorphous germanium, Physica Status Solidi 15 (1966) 627-637. [38] Structural, magnetic, optical properties and cation distribution of nanosized Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) spinel ferrites synthesized by ultrasound irradiation, Ultrasonics Sonochemistry 57 (2019) 203-211.
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[39] S. Güner, Md. Amir, M. Geleri, M. Sertkol, A. Baykal, Magneto-Optical Properties of Mn3+ substituted Fe3O4 Nanoparticle, Ceram. Int., 41 (2015) 10915-10922. [40] Y. Slimani, A. Baykal, Md. Amir, H. Güngüneş, S. Guner, H.S. El Sayed, F. Aldakheel,
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T.A. Saleh, A. Manikandan, Substitution effect of Cr3+ on hyperfine interactions, magnetic and optical properties of Sr-hexaferrites, Ceram. Int. 44 (2018) 15995-16004. [41] I. A. Auwal, H. Güngüneş, S. Güner, Sagar E. Shirsath, M. Sertkol, A. Baykal,
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Structural, magneto-optical properties and cation distribution of SrBixLaxYxFe12−3xO19 (0.0 ≤ x ≤ 0.33) hexaferrites, Mater. Res. Bull. 80 (2016) 263-272.
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[42] K. Kombaiah, J.J. Vijaya, L.J. Kennedy, M. Bououdina, R.J. Ramalingam, H.A. AlLohedan, Comparative investigation on the structural, morphological, optical, and magnetic properties of CoFe2O4 nanoparticles, Ceram. Int. 43 (2017) 7682-7689. [43] T. Tatarchuk, M. Bouodina, W. Macyk, O. Shyichuk, N. Paliychuk, I. Yaremiy, B. Al-
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Najar and M. Pacia, Structural, optical and magnetic properties of Zn-doped CoFe2O4 nanoparticles, Nanoscale Research Lett. 12 (2017) 5-11. [44] R.S. Melo, P. Banerjee, A. Franco Jr, Hydrothermal synthesis of nickel doped ferrite
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nanoparticles: optical and magnetic properties, Journal of Material Science: Materials in Electronics 29 (2018) 14657-14667.
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[45] T.E.P. Alves, H.V.S. Pessoni, A. Franco Jr, The effect of Y3+ subsitution on the structural, optical band-gap, and magnetic properties of Cobalt ferrite nanoparticles, Phys. Chem. Chem. Phys. 19 (2017) 16395. [46 S. Supriya, S. Kumar and M. Kar, Band Gap Engineering of Z substituted Cobalt Ferrite for Optoelectronic Applications, IEEE, Nanotechnology Material and Devices Conference, October 2-4 (2017), Singapore.
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ACCEPTED MANUSCRIPT [47] P. Laokul, S. Arthan, S. Maensiri, E. Swatsitang, Magnetic and Optical Properties of CoFe2O4 Nanoparticles Synthesized by Reverse Micelle Microemulsion Method, J. Supercond. Nov. Magn. 28 (2015) 2483-2489. [48] M. Saha, S. Mukherjee, A. Gayen, Microstructure, optical and magnetic properties of
AOT, J. Aust. Ceram. Soc. 52 (2016) 150-162.
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inverse spinel CoFe2O4 synthesized by microemulsion process assisted by CTAB and
[49] J.L.O. Quinonez, U. Pal, M. S. Villanueva, Structural, Magnetic, and Catalytic
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Evaluation of Spinel, Co, Ni, and Co-Ni Ferrite Nanoparticles Fabricated by LowTemperature Solution Combustion Process, ACS Omega 3 (2018) 14986-15001.
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[50] M.A. Almessiere, Y. Slimani, S. Güner, M. Nawaz, A. Baykal, F. Aldakheel, S. Akhtar, I. Ercan, İ. Belenli, B. Ozçelik, Magnetic and structural characterization of Nb3+substituted CoFe2O4 nanoparticles, Ceram. Int. 45 (2019) 8222-8232. [51] E.C. Stoner, E. Wohlfarth, A mechanism of magnetic hysteresis in heterogeneous alloys,
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Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences 240 (1948) 599-642.
[52] M.A. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Morphology and magnetic
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traits of strontium nanohexaferrites: Effects of manganese/yttrium co-substitution, J. Rare Earths 37 (2019) 732-740.
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[53] M. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Ca2+ and Mg2+ incorporated barium hexaferrites: structural and magnetic properties, J. Sol-Gel Sci. Techn. 88 (2018) 628-638.
[54] M. Almessiere, Y. Slimani, N. Tashkandi, A. Baykal, M. Saraç, A. Trukhanov, İ. Ercan, İ. Belenli, B. Ozçelik, The effect of Nb substitution on magnetic properties of BaFe12O19 nanohexaferrites, Ceram. Int. 45 (2019) 1691-1697.
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ACCEPTED MANUSCRIPT [55] M. Almessiere, Y. Slimani, H. Gungunes, A. Manikandan, A. Baykal, Investigation of the effects of Tm3+ on the structural, microstructural, optical, and magnetic properties of Sr hexaferrites, Results in Physics 13 (2019) 102166. [56] G.V. Duong, N. Hanh, D.V. Linh, R. Groessinger, P. Weinberger, E. Schafler, M.
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Zehetbauer, Monodispersed nanocrystalline Co1–xZnxFe2O4 particles by forced hydrolysis: synthesis and characterization, J. Magn. Magn. Mater. 311 (2007) 46-50. [57] F. Gözüak, Y. Köseoğlu, A. Baykal, H. Kavas, Synthesis and characterization of
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CoxZn1−xFe2O4 magnetic nanoparticles via a PEG-assisted route, J. Magn. Magn. Mater. 321 (2009) 2170-2177.
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[58] Y. Slimani, M. Almessiere, M. Nawaz, A. Baykal, S. Akhtar, I. Ercan, I. Belenli, Effect of bimetallic (Ca, Mg) substitution on magneto-optical properties of NiFe2O4 nanoparticles, Ceram. Int. 45 (2019) 6021-6029.
[59] M. Almessiere, A.D. Korkmaz, Y. Slimani, M. Nawaz, S. Ali, A. Baykal, Magneto-
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optical properties of rare earth metals substituted Co-Zn spinel nanoferrites, Ceram. Int. 45 (2019) 3449-3458.
[60] M. Amir, H. Gungunes, Y. Slimani, N. Tashkandi, H. El Sayed, F. Aldakheel, M.
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Sertkol, H. Sozeri, A. Manikandan, I. Ercan, Mössbauer studies and magnetic properties
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of cubic CuFe2O4 nanoparticles, J. Supercond. Nov. Magn. 32 (2019) 557-564. [61] M. Almessiere, Y. Slimani, S. Güner, A. Baykal, I. Ercan, Effect of dysprosium substitution on magnetic and structural properties of NiFe2O4 nanoparticles, J. Rare Earths 37 (2019) 871-878. [62] M. Almessiere, Y. Slimani, S. Güner, M. Nawaz, A. Baykal, F. Aldakheel, S. Akhtar, I. Ercan, İ. Belenli, B. Ozçelik, Magnetic and structural characterization of Nb3+substituted CoFe2O4 nanoparticles, Ceram. Int. 45 (2019) 8222-8232.
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ACCEPTED MANUSCRIPT [63] Y. Slimani, H. Güngüneş, M. Nawaz, A. Manikandan, H. El Sayed, M. Almessiere, H. Sözeri, S. Shirsath, I. Ercan, A. Baykal, Magneto-optical and microstructural properties of spinel cubic copper ferrites with Li-Al co-substitution, Ceram. Int. 44 (2018) 14242-
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ACCEPTED MANUSCRIPT List of Tables
Table 1. Tb content, refined structural parameters for CoTbxFe2-xO4 (0.00 ≤ x ≤0.10)
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nanospinel ferrites
RBragg
1.95
3.75
8.324(5)
576.87
13.11
1.42
2.59
0.04
8.305(2)
572.86
13.09
0.06
8.308(2)
573.49
11.70
0.08
8.314(1)
574.70
11.46
0.10
8.306(6)
573.16
11.40
V (Å)3
0.00
8.342(1)
0.02
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a (Å)
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χ2(chi2)
580.52
Crystallite Size (nm) ±0.05 14.40
Tb (x)
2.37
4.13
1.67
3.77
1.44
4.39
1.14
2.65
Tetrahedral A-site Co0.15Fe0.85 Co0.15Fe0.75 Co0.15Fe0.75 Co0.15Fe0.75 Co0.16Fe0.76 Co0.17Fe0.74
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x content 0.00 0.02 0.04 0.06 0.08 0.10
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Table 2. Cation distribution of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
Octahedral B-site Co0.85Fe1.15 Co0.85Tb0.02Fe1.13 Co0.85Tb0.04Fe1.11 Co0.85Tb0.06Fe1.09 Co0.84Tb0.08Fe1.08 Co0.83Tb0.1Fe1.07
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x=0.10 (440)
(511)
(422)
(400)
(311)
(220)
Yobs Ycalc Bragg Pos.
(222)
x=0.06
x=0.04
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x=0.02
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Intensity (a. u.)
x=0.08
x=0.00
30
40
50
60
70
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2θ (°)
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Figure 1. XRD powder patterns of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites.
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x=0.10
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Transmission %
x=0.08
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x=0.06
x=0.02
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x=0.00
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x=0.04
1400
1200
1000
800
600
400
Wavenumber (cm-1)
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Figure 2. FT-IR spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
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Figure 3. SEM micrographs CoTbxFe2-xO4 (x=0.00, 0.02, 0.04, 0,08, 0.10) nanospinel ferrites
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Figure 4. The EDX spectra and Elemental mapping results of CoTbxFe2-xO4 (x=0.02, 0.06 and x=0.10) nanospinel ferrites
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CoFe2O4 CoTb0.02Fe1.98O4 CoTb0.04Fe1.96O4 CoTb0.06Fe1.94O4 CoTb0.08Fe1.92O4 CoTb0.10Fe1.90O4
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16 15 14 13 12 200
300
400
500
600
700
800
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Wavelength (nm)
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DR %
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Figure 5. DR % spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
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[F(R ∞ )hν] 2 [eV-cm -1 ] 2
0,030
CoTb0.02Fe1.98O4
CoFe2O4
0,030
0,025
0,025
0,020
0,020
0,015 0,015
0,010
0,005
Eg=1.37 eV
0,000
Eg=1.41 eV
0,000 1
2
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1
2
3
0,035
0,035 0,030
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0,010
Eg=1.37 eV
5
6
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5
6
7
5
6
7
CoTb0.06Fe1.94O4
0,030
0,025
4
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[F(R ∞ )hν]2 [eV-cm -1 ]2
CoTb0.04Fe1.96O4
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0,010
0,005
Eg=1.40 eV
0,005
0,005
0,000
0,000 1
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4
5
0,035
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1
7
2
3
4
0,035
0,030
[F(R ∞ )hν] 2 [eV-cm -1 ] 2
CoTb0.10Fe1.90O4
0,030
CoTb0.08Fe1.92O4
0,025
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0,025
0,020 0,015 0,010 Eg=1.43 eV
0,000 1
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0,005 2
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0,020 0,015 0,010 0,005 Eg=1.44 eV
0,000
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6
7
1
2
3
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Photon Energy (eV)
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Photon Energy (eV)
Figure 6. Tauc plots of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites. Extrapolated linear lines to the straight portion of the spectra intersect the photon energy axis for
[
ℎυ] = 0 and determines the magnitude of Eg.
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(a)
10 0 x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10
-10 -20 -30 -5
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(b)
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H (kOe)
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M (emu/g)
20
0.5
x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10 1.0
H (kOe)
(0.00 ≤ x ≤ 0.10) NPs.
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xO4
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Figure 7. Magnetization against applied magnetic field, M(H), performed at RT of CoTbxFe2-
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Ms (emu/g)
30
(a)
25 20 15 10 0.02
0.04
(b)
4.0 3.5 3.0 2.5 2.0
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1.0 0.8 0.6 0.4 350
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SQR
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(e)
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Tb content (x)
Figure 8. Evolutions of (a) Ms, (b) Mr, (c) substitution content.
3+
, (d) Hc and (e) SQR with respect to Tb3+
3+
substituted Co nanoferrites
A. Sadaqat, M. Almessiere, Y. Slimani, S. Guner, M. Sertkol, H. Albetran, A. Baykal, Sagar E. Shirsath, B. Ozcelik, I. Ercan PII:
S0272-8842(19)32105-4
DOI:
https://doi.org/10.1016/j.ceramint.2019.07.280
Reference:
CERI 22395
To appear in:
Ceramics International
Received Date: 23 May 2019 Revised Date:
23 July 2019
Accepted Date: 24 July 2019
Please cite this article as: A. Sadaqat, M. Almessiere, Y. Slimani, S. Guner, M. Sertkol, H. Albetran, 3+ A. Baykal, S.E. Shirsath, B. Ozcelik, I. Ercan, Structural, optical and magnetic properties of Tb substituted Co nanoferrites prepared via sonochemical approach, Ceramics International (2019), doi: https://doi.org/10.1016/j.ceramint.2019.07.280. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Structural, optical and magnetic properties of Tb3+ substituted Co nanoferrites prepared via sonochemical approach
Baykalg, Sagar E. Shirsathh, B. Ozceliki and I. Ercanb
a
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A. Sadaqata1, M. Almessiereb,c, Y. Slimanib, S. Gunerd, M. Sertkole, H. Albetranf, A.
Department of Mechanical and Energy Engineering, College of Engineering, Imam
Department of Biophysics, Institute for Research and Medical Consultations (IRMC), Imam
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b
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Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia.
Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia. c
Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O.
Box 1982, 31441, Dammam, Saudi Arabia. d
Institute of Inorganic Chemistry, RWTH Aachen University, D-52074 Aachen, Germany.
e
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Deanship of Preparatory Year Building 450, Imam Abdulrahman Bin Faisal University, P.O.
Box 1982, 31441, Dammam, Saudi Arabia. f
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Department of Basic Sciences, College of Education, Imam Abdulrahman Bin Faisal
University, 31451, Dammam, Saudi Arabia. g
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Department of Nanomedicine Research, Institute for Research and Medical Consultations
(IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441, Dammam, Saudi Arabia. h
School of Materials Science and Engineering, University of New South Wales, Kensington,
Sydney, NSW 2052, Australia. i
Department of Physics, Faculty of Science and Letters, Cukurova University, 01330 Balcali,
Adana, Turkey. 1
Corresponding author`s email:[email protected] (Ali Sadaqat). Tel: + 9 66 54 819 862366
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Abstract This paper emphasizes the structure, morphology, optical, and magnetic properties of
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sonochemically prepared terbium-substituted cobalt ferrite nanoparticles, CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10). The formation of cubic spinel nanosized ferrite structure was confirmed by X-ray diffraction (XRD), Field-emission scanning electron microscopy (FE-SEM), and Fourier-
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transform infrared (FT-IR) spectroscopy. The crystallites sizes were found in the range of 11 - 14 nm. Ultraviolet-visible percentage diffuse reflectance investigations were performed on
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pristine and Tb3+-doped cobalt spinel ferrite CoFe2O4 nanoparticles. The direct energy band gap (Eg) values were determined by applying the Kubelka–Munk theory and Tauc plots were found to be in a narrow band range of 1.37 to 1.44 eV. Analyses of magnetization versus the magnetic field (M(H)) were performed. The magnetic parameters, including the saturation ), remanence
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magnetization (Ms), squareness ratio (SQR = Mr/Ms), magnetic moment (
(Mr), and coercivity (Hc) were evaluated. The M(H) curves exhibited a soft ferrimagnetic nature. It was demonstrated that the Tb3+ substitutions strongly influenced the magnetization
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data. Indeed, the Ms, Mr, Hc, and
values decreased with increasing Tb3+ substitution.
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Keywords: Spinel ferrite; Structure; Cation distribution; Microstructure; Optical properties; Magnetic properties.
1. Introduction Spinel ferrite nanoparticles (MFe2O4) play a very important role in industrial and scientific applications [1–2], such as magneto-strictive sensors, actuators, drug delivery, gas sensors, solar cells, memory devices, transducers, hyperthermia, supercapacitors, spintronic devices,
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ACCEPTED MANUSCRIPT and microwaves [3–7]. Cobalt nanospinel ferrites, such as CoFe2O4, have the most favorable ferrimagnetic materials, exhibiting exceptional properties, and are based on the grains size and cation distributions at the tetrahedral 64 A-sites and octahedral 32 B-sites in the spinel ferrite structure [7–9]. Cobalt spinel ferrite is used extensively owing to certain beneficial
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features, including high magneto-crystalline anisotropy, chemical stability, coercivity (Hc), saturation magnetization (Ms), and high Curie temperature [10–11]. Many researchers have demonstrated the chemical, dielectric, physical, optical, and magnetic characteristics based on
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cation substitution and synthesized materials. Numerous techniques are applied to synthesize spinel ferrite nanoparticles, such as the co-precipitation method, sol-gel auto-combustion
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technique, solvothermal method, micro-emulsion method, and hydrothermal method [12–14]. Rare earth (RE) ions play a very important role in changing the ferrite structure, owing to their large radius and stable valency. In recent years, the physical properties have been improved by substituting RE ions into the spinel ferrite nanostructure [15–16]. Nanospinel
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ferrites are very helpful in controlling the electromagnetic pollution, with their significant resistivities and magnetic losses operating as electromagnetic wave-absorbing materials [17]. RE substitution has an excellent effect on controlling the electromagnetic and
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crystallographic properties in the spinel ferrite structure. RE oxides are used as electrical
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insulators owing to their excellent resistivity (106 Ω.cm) at room temperature [18–20]. The lanthanides series Pr, Pm, Dy, Y, Nd, Sm, Ce, Er, and La play a significant role in substitution of the ferrites structure [21]. The ionic radii and magnetic parameters can be controlled with the addition of RE in spinel ferrites [22]. RE ions have a significant effect in modifying the electromagnetic traits of ferrites, which is the reason for the strong spin-orbit couplings of unpaired 4f electrons. The electromagnetic properties exhibit a strong influence and interaction between RE and Fe (3d–4f coupling) in nanoferrites [23, 24]. The sol-gel auto-combustion process was employed to produce CoxZnxGdxFe2−xO4 nanoparticles, and the
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ACCEPTED MANUSCRIPT electrical and elastic properties by substitution of Gd3+ ions in cobalt-zinc ferrite were studied [25]. Pachpinde et al. [26] synthesized PrxCoFe2−xO4 nanoparticles in a sol-gel autocombustion method and noted that the saturation magnetization was improved with the substitution of Pr3+ in cobalt spinel ferrites. Singh et al. [27] observed that the coercive field
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(Hc) and saturation magnetization (Ms) values were decreased with an increase of the RE (Pr, Sm, and La) contents in Ni-Zn nanoferrites. Materials of NixZnxFe1.95RxO4 were prepared by the citrate precursor process and also annealed at 450 °C. Finally, the process was noted as
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highly valuable for recording and microwave applications. Almessiere et al. [28] prepared a CoTmxFe2−xO4 (0.0 ≤ x ≤ 0.08) nanocomposite using the sonochemical approach. In this
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study, it was observed that the Hc and Ms values were improved with the doping of Tm3+ into Co-spinel ferrites. Abdellahi et al. [29] reported that the permeability decreased and resistivity increased with the addition of Tb3+-doped nanocrystalline NiCuZn nanoferrite particles.
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To the best of our knowledge, the series of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles were synthesized via sonochemical method for the first time in this study. The impact of Tb3+ ion substitution on the microstructure, morphology, spectral, optical and
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magnetic properties of spinel CoFe2O4 ferrites was deeply investigated.
2. Experiment
The sonochemical method was employed to fabricate CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles. Cobalt nitrate hexahydrate (Co(NO3)2·6H2O), iron (III) nitrate nonahydrate ((Fe(NO3)3·9H2O), and terbium oxide (Tb4O7) were utilized as the starting materials. A specific amount of salt nitrite was dissolved in deionized (DI) water, which formed the first solution. The second solution was Tb4O7 dissolved in 10 ml of concentrated HCl at 180 °C. The two solutions were mixed together, and the pH was adjusted to 11 by using 2 M of
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ACCEPTED MANUSCRIPT NaOH solution. The resulting solution was exposed to ultrasonic irradiation for 60 min. The powder was washed frequently with DI water. The magnetic powder was detached from the mixture by an outer magnet, and then dried at 60 °C for 12 h. The structure was analyzed using the Rigaku Benchtop Miniflex X-ray diffraction (XRD)
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with CuKα radiation. A Field-emission scanning electron microscope (FE-SEM; FEI Titan ST) coupled with an energy dispersive X-rays (EDX) spectrometer system was utilized for the surface morphology and chemical compositions. The Fourier-transform infrared (FT-IR)
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spectra were restarted using a wavelength range from 4000 to 400 cm−1. The magnetic properties were determined using a superconducting quantum interference device (SQUID)
3. Results and discussion 3.1. Structural
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from Quantum Design coupled with a vibrating sample magnetometer (VSM) head.
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The XRD powder patterns of the CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles are illustrated in Figure 1. All X-ray peaks correspond to the spinel cubic structure, which refers to the Fd3m space group symmetry. Furthermore, there is no indication of any second phase, which
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proves that all specimens were pure and of a single spinel structure. The XRD peak at (311)
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was shifted in the direction of lower diffraction angles with the addition of the Tb content. This shifting was caused by the disordering of the spinel lattice. Software (Match3!) was used to evaluate the crystallite size and lattice parameters (Table 1). It was demonstrated that the lattice parameters were reduced from x = 0.00 to x = 0.04 and the remaining ratios were increased. This diversity could be attributed to the larger ionic radii of Tb3+ (1.06 Å) compared to Co2+ (0.745 Å) and Fe3+ (0.645 Å). The lattice was broadened as a consequence of the distortion in the lattice [30,31]. The crystallite size of all compositions was almost constant, between 11 and 14 nm (Table 1), owing to the stability of the full width at half
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Figure 1.
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3.2. FT-IR
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the preference of Tb3+ ions is Oh sites [32].
Figure 2 displayed FT-IR spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) NPs. All compositions
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presented FT-IR absorption bands at 579 and 407 cm-1 (the respective vibrational modes of Me-O (metal-oxide), similar to the vibration bands of tetrahedral and octahedral sites individually [33-35]. It has been notice that the substitution of the Tb3+ ion into the cobalt ferrite has to some extent shifted peaks in the direction of the higher frequency side. The
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shifting of peaks has been indicate the micro-strain in the cobalt ferrite lattices reason by the larger sized Tb3+ ion substitution and changing in the distance of iron oxygen bond. Furthermore, the intensity of the peaks (574 cm−1) vibrational mode is slowly increased with
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increasing Tb3+ substitution [36].
Figure 2.
3.3. Morphology
FE-SEM images of the different nanoparticles are presented in Figure 3. The micrographs exhibited a high degree of aggregation of the spherical nanoparticles because of the high magnetization of the spinel ferrite [38]. The particle size was found to be less than 20 nm for all compositions, with no substantial modification when increasing the Tb substitution, as illustrated in Figure 1, which was confirmed by the XRD analysis. The EDX and elemental
6
ACCEPTED MANUSCRIPT mapping verified the presence of elements consisting of Tb substituted Co-nanoferrites (Figure 4).
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Figure 3.
Figure 4.
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3.4. Optical
Percent diffuse reflectance (DR %) measurements were performed on the CoTbxFe2-xO4 (x =
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0.00 to 0.10) nanospinel ferrites using an ultraviolet-visible (UV-Vis) spectrophotometer in a sweep range of 200 to 800 nm. The recorded spectra are displayed in Figure 5. The DR % magnitudes exhibited an intensity band of 12% to 15% in the near UV (200 to 380 nm) and visible (380 to 740 nm) regions of electromagnetic radiation. Above 740 nm, the reflectance
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intensities increased slightly in the remaining sweep range of the spectrophotometer. The optical energy band gap (Eg) values were calculated as follows [37-41]:
where
=
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=
is the Kubelka–Munk function,
(1) provides the DR ratio between
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the measured and reference samples, A is a constant of proportionality, hυ is the incident photon energy, and the exponent n is related to the types of electronic transitions. Exponent values of n = 1/2 and n = 2 correspond to direct and indirect allowed transitions, respectively. Therefore, the direct Eg values belonging to each sample were determined by extrapolating the linear part of the [
ℎυ]2 versus photon energy plots for [
ℎυ] = 0 eV. These
plots are also known as Tauc plots, and the extrapolated Eg values are presented in Figure 6 for all the CoTbxFe2-xO4 (x = 0.00 to 0.10) nanospinel ferrites. All of the Tauc plots had yaxis exponents equal to 2 and this case assigned the direct allowed transitions for the undoped 7
ACCEPTED MANUSCRIPT and Tb3+ doped nanoparticles. The estimated band gap of pristine CoFe2O4 is 1.37 eV. Comparing this value with the estimated energy band gaps of the doped nanospinel ferrites, it can easily be observed that the Tb3+ ions caused slight increments until the maximum band gap of 1.44 eV belonging to the CoTb0.10Fe1.90O4 nanospinel ferrites. The order of the Eg
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values reveals the semiconducting nature of all the samples. In the literature, direct or indirect Eg data are reported for pristine and doped cobalt ferrites with different elements, such as Zn, Ni, Y, and Nb [42-50]. The reported Eg magnitudes for direct or indirect allowed transitions
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are within a wide range between 0.48 and 4.3 eV. In the literature, Tatarchuk et al. and
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Quinonez et al. reported the closest data to our direct optical Eg values [42, 45].
Figure 5.
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3.5. Magnetization
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Figure 6.
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Figure 7 illustrates the magnetization as a function of applied magnetic field, M(H), hysteresis loops for various CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanoparticles. It is obvious that the Tb3+ substitutions in the Fe3+ sites played a significant role in developing the magnetic properties of the CoFe2O4. The Stoner–Wohlfarth (S–W) methodology was employed to deduce the saturation magnetization (Ms) values [51-55]. The synthesized nanoparticles exhibited saturation magnetization (Ms), remanant magnetization (Mr), and coercive field (Hc) magnitudes in the ranges of 9.1 to 26.7 emu/g, 2.33 to 4.22 emu/g, and 199.4 to 317.6
8
ACCEPTED MANUSCRIPT Oe, respectively. These values demonstrate the soft ferrimagnetic nature of different CoTbxFe2-xO4 nanoparticles at room temperature.
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Figure 7.
The impact of the Tb3+ substitutions on the Ms, Mr, and Hc of the studied CoTbxFe2xO4
nanoparticles were evaluated. The pristine CoFe2O4 (x = 0.00) sample exhibited Ms
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values equal to 26.7 emu/g. The obtained magnitude was lower than that of the bulk CoFe2O4 (Ms ~ 80 emu/g) [56,57], which was primarily attributed to the presence of tinier nano-
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crystallites in the sample. In fact, this would lead to spins disordering through a large surfaceto-volume ratio [58], thereby lowering the Ms. The occurrences of canted spins owing to competitive antiferromagnetic interactions and the resultant disordered distribution of cations on the sample surface could be responsible for the reduced Ms value [59,60]. The Ms and Mr
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values for the various proposed compositions exhibited a diminishing trend with the increase in the Eu3+ concentration, wherein the Ms and Mr were lowest for the sample with x = 0.10. Both the Ms and Mr followed the same tendency with an increasing Tb3+ doping content [59].
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Various studies have suggested that the change in the magnetic traits of doped spinel
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nanoferrites are governed by the presence of strains, variations in grains sizes and their distributions, strength of the super-exchange interaction, and variations in
. The reduction
in the Ms values with the reduction in the grain size has been described in several investigations [61,62]. Here, the reduction in the Ms and Mr values with the increase in Tb3+ content agreed with the XRD findings, which demonstrated a reduction in the crystallite sizes, and therefore a reduction in the magnetizations. Furthermore, the substitution of Fe3+ with ionic radii of 0.645 Å by Tb3+ ions with larger ionic radii (1.06 Å) could create local strains and disorder in the ferrite system, which would alter the electronic states and magnetic
9
ACCEPTED MANUSCRIPT traits. Moreover, it has been reported that the relation between magnetic moment (
) and
saturation magnetization (Ms) can be expressed as [58,53]: !" # $% & ' ( . ))*)
=
for the synthesized
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Figure 8(c) displays the Tb3+ content dependent variation in the nanoparticles. Generally, the decrease in
is resulted from the weakening of the super-
exchange interactions among various sites. In the present study, the x = 0.00 composition decreases with increasing Tb3+ substitution
and Ms.
content. The observed reduction in the
values is attributed to the weakening of the super-
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exhibited maximum values of
shows similar lowering
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exchange coupling among various lattice sites. The evolution of
tendency to that of Ms and Mr when the Tb3+ content increases. The squareness ratio (SQR) values were also determined and are presented in Figure 8(e). The SQR values for nanoferrites with cubic and uniaxial anisotropy are generally known to be close to 0.83 and 0.50, respectively [58,63]. If the SQR is equal to or above 0.5, nanoparticles are known to
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exist in multiple magnetic domain structures [58,63]. However, if the SQR is below 0.5, the nanoparticles are known to occur in a single magnetic domain (SMD) structures [55, 60]. For
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the various synthesized nanoparticles, the SQR values obtained suggest a uniaxially anisotropic SMD character. It is worth noting that SQR values below than 0.5 signify the
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presence of strong surface spin disordering [58,63].
Figure 8.
4. Conclusion
The influence of Tb3+ substitution on the structural, morphology, optical and magnetic properties of cobalt ferrite nanoparticles, CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10), synthesized by the sonochemical approach was examined in detail. The incorporated Tb3+ in the spinel structure was verified by XRD. The DXRD values were found to be in the range of 11 to 14 nm. FE10
ACCEPTED MANUSCRIPT SEM investigations revealed a spherical structure and particles size that correspond with the XRD analysis. The direct Eg estimated from DR % data are found in the range of 1.37 to 1.44 eV, revealing the semiconductor characteristics of all nanoparticles. The Eg values increased slightly owing to the Tb3+ ion doping process. M(H) analyses showed soft ferrimagnetic
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behavior for various nanoparticles. The values of magnetic parameters, Ms, Mr, and
, for
the synthesized nanoparticles were decreased with the increase in Tb3+ substitution contents. Such observations could be attributed to the presence of strains, weakening of the super-
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exchange interaction, reduction in crystallites size, surface spin disorder, and reduction in
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magnetic moment.
Acknowledgements
This study was supported by the Deanship for Scientific Research (project applications 2017576-IRMC and 2018-209-IRMC) of Imam Abdulrahman Bin Faisal University (Saudi
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References
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Arabia).
[1] S. Karimunnesa, A.K.M.A. Ullah, M.R. Hasan, F.S. Shanta, R. Islam, M.N.I. Khan,
AC C
Effect of holmium substitution on the structural, magnetic and transport properties of CoFe2-xHoxO4 ferrites, J. Magn. Magn. Mater. 457 (2018) 57–63. [2] S.K. Gore, R.S. Mane, M. Naushad, S.S. Jadhav, Influence of Bi3+-doping on the magnetic and Mössbauer properties of spinel cobalt ferrite, (2015) 6384–6390. [3] A.A. Khan, U. Hira, Z. Iqbal, M. Usman, F. Sher, Structural, magnetic and magnetocaloric properties of CoFe2−xMoxO4 (0.0≤x≤0.3) ferrites, Ceram. Int. 43 (2017) 7088–7093.
11
ACCEPTED MANUSCRIPT [4] M.S. Hossain, B. Alam, M. Shahjahan, Synthesis, structural investigation, dielectric and magnetic properties of Zn2+-doped cobalt ferrite by the sol – gel technique, J. Adv. Dielectrics 8 (2018) 2–7. [5] M. Gharibshahian, M.S. Nourbakhsh, O. Mirzaee, Evaluation of the superparamagnetic
RI PT
and biological properties of microwave assisted synthesized Zn & Cd doped CoFe2O4 nanoparticles via Pechini sol--gel method, J. Sol-Gel Sci. Technol. 85 (2018) 684–692. [6] M. Ansari, A. Bigham, S.A. Hassanzadeh-Tabrizib, H. Abbastabar Ahangar, Synthesis
system, J. Magn. Magn. Mater. 439 (2017) 67-75.
SC
and characterization of Cu0.3Zn0.5Mg0.2Fe2O4 nanoparticlesas a magnetic drug delivery
M AN U
[7] M.K. Zate, V. V Jadhav, S.K. Gore, J.H. Shendkar, S.U. Ekar, A. Al-Osta, M. Naushad, R.S. Mane, Structural, morphological and electrochemical supercapacitive properties of sprayed manganese ferrite thin film electrode, J. Anal. Appl. Pyrolysis. 122 (2016) 224– 229.
TE D
[8] R.H. Kodama, A.E. Berkowitz, E.J. McNiff, S. Foner, Surface spin disorder in ferrite nanoparticles, J. Appl. Phys. 81 (1998) 5552. [9] M.A. Almessiere, Y. Slimani, A.D. Korkmaz, N. Taskhandi, M. Sertkol, A. Baykal, Sagar
EP
E. Shirsath, İ. Ercan, B. Ozçelik, Sonochemical synthesis of Eu3+ substituted CoFe2O4
AC C
nanoparticles and their structural, optical and magnetic properties, Ultrasonics Sonochemistry 58 (2019) 104621. [10] N. Kasapoğlu, A. Baykal, Y. Köseoğlu, M.S. Toprak, Microwave-assisted Combustion Synthesis of CoFe2O4 with Urea and its magnetic Characterization, Scriptia Materialia, 57 (2007) 441-444. [11] D.L. Zhao, Fabrication and microwave absorbing properties of Ni–Zn nanospinel ferrites, J. Alloys Compd. 480 (2009) 634–638.
12
ACCEPTED MANUSCRIPT [12] Y. Slimani, M.A. Almessiere, M. Nawaz, A. Baykal, S.Akhtar, I. Ercan, I. Belenli, Effect of bimetallic (Ca, Mg) substitution on magneto-optical properties of NiFe2O4 nanoparticles, Cer Int 45 (2019) 6021-6029. [13] F. Li, J. Liu, D.G. Evans, X. Duan, Stoichiometric Synthesis of Pure MFe2O4 (M = Mg,
RI PT
Co, and Ni) Nanospinel ferrites from Tailored Layered Double Hydroxide (Hydrotalcite-Like) Precursors, Chem. Mater. 16 (2004) 1597–1602.
[14] M.M.L. Sonia, S. Anand, V.M. Vinosel, M.A. Janifer, S. Pauline, A. Manikandan, Effect
SC
of lattice strain on structure, morphology and magneto-dielectric properties of spinel
Mater. 466 (2018) 238–251.
M AN U
NiGdxFe2−xO4 ferrite nano-crystallites synthesized by sol-gel route, J. Magn. Magn.
[15] M. Akhtar, M. Khan, Effect of rare earth doping on the structuraland magnetic features of nanocrystalline nanospinel ferrites prepared via sol gel route, J. Magn. Magn. Mater. 460 (2018) 12111–12111.
TE D
[16] C. Srinivas, Structural and magnetic characterization of co-precipitated NixZn1−xFe2O4 ferrite nanoparticles, J. Magn. Magn. Mater. 407 (2016) 135–141. [17] C. Stergiou, Magnetic, dielectric and microwave absorption properties of rare earth
AC C
629–635.
EP
doped Ni–Co and Ni–Co–Zn nanospinel ferrites, J. Magn. Magn. Mater. 426 (2017)
[18] M. Ajmal, The influence of Ga doping on structural magnetic and dielectric properties of NiCr0.2Fe1.8O4 spinel ferrite, Physica B. Condens. Matter. 526 (2017) 149–154. [19] N. Lwin, M.N.A. Fauzi, S. Sreekantan, R. Othman, Physical and electromagnetic properties of nanosized Gd substituted Mg–Mn ferrites by solution combustion method, Phys. B Condens. Matter. 461 (2015) 134–139. [20] A.A. Sattar, A.H. Wafik, K.M. El-shokrofy, Magnetic Properties of Cu ± Zn Ferrites Doped with Rare Earth Oxides, phys. stat. sol. (a) 563 (1999) 563–570.
13
ACCEPTED MANUSCRIPT [21] K. V Zipare, S.S. Bandgar, G.S. Shahane, Effect of Dy-substitution on structural and magnetic properties of MnZn ferrite nanoparticles, J. Rare Earths. 36 (2018) 86–94. [22] M.H. Abdellatif, Magnetic characterization of rare earth doped spinel ferrite, J. Magn. Magn. Mater. 442 (2017) 445–452.
RI PT
[23] M. Hashim, M. Raghasudha, S.S. Meena, J. Shah, S.E. Shirsath, S. Kumar, D. Ravinder, P. Bhatt, Alimuddin, R. Kumar, R.K. Kotnala, Influence of rare earth ion doping (Ce and Dy) on electrical and magnetic properties of cobalt ferrites, J. Magn. Magn. Mater. 449
SC
(2018) 319–327.
[24] G. Dascalu, Structural, electric and magnetic properties of CoFe1.8RE0.2O4 (RE=Dy, Gd,
M AN U
La) bulk materials, J. Magn. Magn. Mater. 333 (2013) 69–74.
[25] R.A. Pawar, S.S. Desai, S.M. Patange, S.S. Jadhav, K.M. Jadhav, Inter-atomic bonding and dielectric polarization in Gd3+ incorporated Co-Zn ferrite nanoparticles, Phys. B Condens. Matter. 510 (2017) 74–79.
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[26] A.M. Pachpinde, Impact of larger rare earth Pr3+ ions on the physical properties of chemically derived PrxCoFe2−xO4 nanoparticles, Chem. Phys. 429 (2014) 20–26. [27] R.K. Singh, Magnetic and dielectric properties of rare earth substituted
EP
Ni0.5Zn0.5Fe1.95R0.05O4 (R = Pr, Sm and La) ferrite nanoparticles, Mater. Sci. Eng. B 210
AC C
(2016) 64–69.
[28] M.A. Almessiere, Y. Slimani, A.D. Korkmaz, S. Guner, M. Sertkol, S.E. Shirsath, A. Baykal, Structural, optical and magnetic properties of Tm3+ substituted cobalt nanospinel ferrites synthesized via sonochemical approach, Ultrason. Sonochem. 54 (2019) 1-10. [29] S.M. Kabbur, S.D. Waghmare, D.Y. Nadargi, S.D. Sartale, R.C. Kambale, U.R. Ghodake, S.S. Suryavanshi, Magnetic interactions and electrical properties of Tb3+ substituted NiCuZn ferrites, J. Magn. Magn. Mater. 473 (2019) 99–108.
14
ACCEPTED MANUSCRIPT [30] S.D. Bhame, P.A. Joy, Magnetoelastic properties of terbium substituted cobalt ferrite, Chem. Phys. Lett. 685 (2017) 465–469. [31] G. Bulai, L. Diamandescu, I. Dumitru, S. Gurlui, M. Feder, O.F. Caltun, Effect of rare earth substitution in cobalt ferrite bulk materials, J. Magn. Magn. Mater. 390 (2015)
RI PT
123–131.
[32] V.S. Puli, S. Adireddy, C.V Ramana, Chemical bonding and magnetic properties of gadolinium (Gd) substituted cobalt ferrite, J. Alloys Compd. 644 (2015) 470–475.
SC
[33] B. Labde, M.C. Sable, N. Shamkuwar, Structural and infra-red studies of Ni1+xPbxFe2−2xO4 system, Mater. Lett. 57 (2003) 1651–1655.
M AN U
[34] M.A. Almessiere, Y. Slimani, S. Guner, M. Sertkol, A. Demir Korkmaz, Sagar E. Shirsath, A. Baykal, Sonochemical synthesis and physical properties of Co0.3Ni0.5Mn0.2EuxFe2−xO4 nano-spinel ferrites, Ultrasonics Sonochemistry 58 (2019) 104654.
TE D
[35] A. Baykal, N. Kasapoglu, Y. Koseoglu, M.S. Toprak, H. Bayrakdar, CTAB-assisted hydrothermal synthesis of NiFe2O4 and its magnetic characterization, J. Alloys Compd. 464 (2008) 514–518.
EP
[36] R. Sharma, S. Bansal, S. Singhal, Augmenting the catalytic activity of CoFe2O4 by
AC C
substituting rare earth cations into the spinel structure, RSC Adv. 6 (2016) 71676– 71691.
[37] J. Tauc, R. Grigorovici, A. Vancu, Optical properties and electronic structure of amorphous germanium, Physica Status Solidi 15 (1966) 627-637. [38] Structural, magnetic, optical properties and cation distribution of nanosized Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) spinel ferrites synthesized by ultrasound irradiation, Ultrasonics Sonochemistry 57 (2019) 203-211.
15
ACCEPTED MANUSCRIPT
[39] S. Güner, Md. Amir, M. Geleri, M. Sertkol, A. Baykal, Magneto-Optical Properties of Mn3+ substituted Fe3O4 Nanoparticle, Ceram. Int., 41 (2015) 10915-10922. [40] Y. Slimani, A. Baykal, Md. Amir, H. Güngüneş, S. Guner, H.S. El Sayed, F. Aldakheel,
RI PT
T.A. Saleh, A. Manikandan, Substitution effect of Cr3+ on hyperfine interactions, magnetic and optical properties of Sr-hexaferrites, Ceram. Int. 44 (2018) 15995-16004. [41] I. A. Auwal, H. Güngüneş, S. Güner, Sagar E. Shirsath, M. Sertkol, A. Baykal,
SC
Structural, magneto-optical properties and cation distribution of SrBixLaxYxFe12−3xO19 (0.0 ≤ x ≤ 0.33) hexaferrites, Mater. Res. Bull. 80 (2016) 263-272.
M AN U
[42] K. Kombaiah, J.J. Vijaya, L.J. Kennedy, M. Bououdina, R.J. Ramalingam, H.A. AlLohedan, Comparative investigation on the structural, morphological, optical, and magnetic properties of CoFe2O4 nanoparticles, Ceram. Int. 43 (2017) 7682-7689. [43] T. Tatarchuk, M. Bouodina, W. Macyk, O. Shyichuk, N. Paliychuk, I. Yaremiy, B. Al-
TE D
Najar and M. Pacia, Structural, optical and magnetic properties of Zn-doped CoFe2O4 nanoparticles, Nanoscale Research Lett. 12 (2017) 5-11. [44] R.S. Melo, P. Banerjee, A. Franco Jr, Hydrothermal synthesis of nickel doped ferrite
EP
nanoparticles: optical and magnetic properties, Journal of Material Science: Materials in Electronics 29 (2018) 14657-14667.
AC C
[45] T.E.P. Alves, H.V.S. Pessoni, A. Franco Jr, The effect of Y3+ subsitution on the structural, optical band-gap, and magnetic properties of Cobalt ferrite nanoparticles, Phys. Chem. Chem. Phys. 19 (2017) 16395. [46 S. Supriya, S. Kumar and M. Kar, Band Gap Engineering of Z substituted Cobalt Ferrite for Optoelectronic Applications, IEEE, Nanotechnology Material and Devices Conference, October 2-4 (2017), Singapore.
16
ACCEPTED MANUSCRIPT [47] P. Laokul, S. Arthan, S. Maensiri, E. Swatsitang, Magnetic and Optical Properties of CoFe2O4 Nanoparticles Synthesized by Reverse Micelle Microemulsion Method, J. Supercond. Nov. Magn. 28 (2015) 2483-2489. [48] M. Saha, S. Mukherjee, A. Gayen, Microstructure, optical and magnetic properties of
AOT, J. Aust. Ceram. Soc. 52 (2016) 150-162.
RI PT
inverse spinel CoFe2O4 synthesized by microemulsion process assisted by CTAB and
[49] J.L.O. Quinonez, U. Pal, M. S. Villanueva, Structural, Magnetic, and Catalytic
SC
Evaluation of Spinel, Co, Ni, and Co-Ni Ferrite Nanoparticles Fabricated by LowTemperature Solution Combustion Process, ACS Omega 3 (2018) 14986-15001.
M AN U
[50] M.A. Almessiere, Y. Slimani, S. Güner, M. Nawaz, A. Baykal, F. Aldakheel, S. Akhtar, I. Ercan, İ. Belenli, B. Ozçelik, Magnetic and structural characterization of Nb3+substituted CoFe2O4 nanoparticles, Ceram. Int. 45 (2019) 8222-8232. [51] E.C. Stoner, E. Wohlfarth, A mechanism of magnetic hysteresis in heterogeneous alloys,
TE D
Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences 240 (1948) 599-642.
[52] M.A. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Morphology and magnetic
EP
traits of strontium nanohexaferrites: Effects of manganese/yttrium co-substitution, J. Rare Earths 37 (2019) 732-740.
AC C
[53] M. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Ca2+ and Mg2+ incorporated barium hexaferrites: structural and magnetic properties, J. Sol-Gel Sci. Techn. 88 (2018) 628-638.
[54] M. Almessiere, Y. Slimani, N. Tashkandi, A. Baykal, M. Saraç, A. Trukhanov, İ. Ercan, İ. Belenli, B. Ozçelik, The effect of Nb substitution on magnetic properties of BaFe12O19 nanohexaferrites, Ceram. Int. 45 (2019) 1691-1697.
17
ACCEPTED MANUSCRIPT [55] M. Almessiere, Y. Slimani, H. Gungunes, A. Manikandan, A. Baykal, Investigation of the effects of Tm3+ on the structural, microstructural, optical, and magnetic properties of Sr hexaferrites, Results in Physics 13 (2019) 102166. [56] G.V. Duong, N. Hanh, D.V. Linh, R. Groessinger, P. Weinberger, E. Schafler, M.
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Zehetbauer, Monodispersed nanocrystalline Co1–xZnxFe2O4 particles by forced hydrolysis: synthesis and characterization, J. Magn. Magn. Mater. 311 (2007) 46-50. [57] F. Gözüak, Y. Köseoğlu, A. Baykal, H. Kavas, Synthesis and characterization of
SC
CoxZn1−xFe2O4 magnetic nanoparticles via a PEG-assisted route, J. Magn. Magn. Mater. 321 (2009) 2170-2177.
M AN U
[58] Y. Slimani, M. Almessiere, M. Nawaz, A. Baykal, S. Akhtar, I. Ercan, I. Belenli, Effect of bimetallic (Ca, Mg) substitution on magneto-optical properties of NiFe2O4 nanoparticles, Ceram. Int. 45 (2019) 6021-6029.
[59] M. Almessiere, A.D. Korkmaz, Y. Slimani, M. Nawaz, S. Ali, A. Baykal, Magneto-
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optical properties of rare earth metals substituted Co-Zn spinel nanoferrites, Ceram. Int. 45 (2019) 3449-3458.
[60] M. Amir, H. Gungunes, Y. Slimani, N. Tashkandi, H. El Sayed, F. Aldakheel, M.
EP
Sertkol, H. Sozeri, A. Manikandan, I. Ercan, Mössbauer studies and magnetic properties
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of cubic CuFe2O4 nanoparticles, J. Supercond. Nov. Magn. 32 (2019) 557-564. [61] M. Almessiere, Y. Slimani, S. Güner, A. Baykal, I. Ercan, Effect of dysprosium substitution on magnetic and structural properties of NiFe2O4 nanoparticles, J. Rare Earths 37 (2019) 871-878. [62] M. Almessiere, Y. Slimani, S. Güner, M. Nawaz, A. Baykal, F. Aldakheel, S. Akhtar, I. Ercan, İ. Belenli, B. Ozçelik, Magnetic and structural characterization of Nb3+substituted CoFe2O4 nanoparticles, Ceram. Int. 45 (2019) 8222-8232.
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ACCEPTED MANUSCRIPT [63] Y. Slimani, H. Güngüneş, M. Nawaz, A. Manikandan, H. El Sayed, M. Almessiere, H. Sözeri, S. Shirsath, I. Ercan, A. Baykal, Magneto-optical and microstructural properties of spinel cubic copper ferrites with Li-Al co-substitution, Ceram. Int. 44 (2018) 14242-
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Table 1. Tb content, refined structural parameters for CoTbxFe2-xO4 (0.00 ≤ x ≤0.10)
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nanospinel ferrites
RBragg
1.95
3.75
8.324(5)
576.87
13.11
1.42
2.59
0.04
8.305(2)
572.86
13.09
0.06
8.308(2)
573.49
11.70
0.08
8.314(1)
574.70
11.46
0.10
8.306(6)
573.16
11.40
V (Å)3
0.00
8.342(1)
0.02
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a (Å)
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χ2(chi2)
580.52
Crystallite Size (nm) ±0.05 14.40
Tb (x)
2.37
4.13
1.67
3.77
1.44
4.39
1.14
2.65
Tetrahedral A-site Co0.15Fe0.85 Co0.15Fe0.75 Co0.15Fe0.75 Co0.15Fe0.75 Co0.16Fe0.76 Co0.17Fe0.74
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x content 0.00 0.02 0.04 0.06 0.08 0.10
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Table 2. Cation distribution of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
Octahedral B-site Co0.85Fe1.15 Co0.85Tb0.02Fe1.13 Co0.85Tb0.04Fe1.11 Co0.85Tb0.06Fe1.09 Co0.84Tb0.08Fe1.08 Co0.83Tb0.1Fe1.07
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x=0.10 (440)
(511)
(422)
(400)
(311)
(220)
Yobs Ycalc Bragg Pos.
(222)
x=0.06
x=0.04
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x=0.02
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Intensity (a. u.)
x=0.08
x=0.00
30
40
50
60
70
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2θ (°)
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Figure 1. XRD powder patterns of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites.
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x=0.10
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Transmission %
x=0.08
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x=0.06
x=0.02
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x=0.00
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x=0.04
1400
1200
1000
800
600
400
Wavenumber (cm-1)
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Figure 2. FT-IR spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
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Figure 3. SEM micrographs CoTbxFe2-xO4 (x=0.00, 0.02, 0.04, 0,08, 0.10) nanospinel ferrites
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Figure 4. The EDX spectra and Elemental mapping results of CoTbxFe2-xO4 (x=0.02, 0.06 and x=0.10) nanospinel ferrites
ACCEPTED MANUSCRIPT 19
CoFe2O4 CoTb0.02Fe1.98O4 CoTb0.04Fe1.96O4 CoTb0.06Fe1.94O4 CoTb0.08Fe1.92O4 CoTb0.10Fe1.90O4
18
16 15 14 13 12 200
300
400
500
600
700
800
SC
Wavelength (nm)
RI PT
DR %
17
AC C
EP
TE D
M AN U
Figure 5. DR % spectra of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites
ACCEPTED MANUSCRIPT 0,035
[F(R ∞ )hν] 2 [eV-cm -1 ] 2
0,030
CoTb0.02Fe1.98O4
CoFe2O4
0,030
0,025
0,025
0,020
0,020
0,015 0,015
0,010
0,005
Eg=1.37 eV
0,000
Eg=1.41 eV
0,000 1
2
3
4
5
6
7
1
2
3
0,035
0,035 0,030
0,020
0,020
0,015
0,015
0,010
M AN U
0,025
0,010
Eg=1.37 eV
5
6
7
5
6
7
5
6
7
CoTb0.06Fe1.94O4
0,030
0,025
4
SC
[F(R ∞ )hν]2 [eV-cm -1 ]2
CoTb0.04Fe1.96O4
RI PT
0,010
0,005
Eg=1.40 eV
0,005
0,005
0,000
0,000 1
2
3
4
5
0,035
6
1
7
2
3
4
0,035
0,030
[F(R ∞ )hν] 2 [eV-cm -1 ] 2
CoTb0.10Fe1.90O4
0,030
CoTb0.08Fe1.92O4
0,025
TE D
0,025
0,020 0,015 0,010 Eg=1.43 eV
0,000 1
EP
0,005 2
3
4
0,020 0,015 0,010 0,005 Eg=1.44 eV
0,000
5
6
7
1
2
3
4
Photon Energy (eV)
AC C
Photon Energy (eV)
Figure 6. Tauc plots of CoTbxFe2-xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites. Extrapolated linear lines to the straight portion of the spectra intersect the photon energy axis for
[
ℎυ] = 0 and determines the magnitude of Eg.
ACCEPTED MANUSCRIPT 30
(a)
10 0 x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10
-10 -20 -30 -5
15
(b)
5
M AN U
10
M (emu/g)
0
H (kOe)
5 0 -5
TE D
-10 -15 -1.0
-0.5
0.0
10
SC
-10
RI PT
M (emu/g)
20
0.5
x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10 1.0
H (kOe)
(0.00 ≤ x ≤ 0.10) NPs.
AC C
xO4
EP
Figure 7. Magnetization against applied magnetic field, M(H), performed at RT of CoTbxFe2-
ACCEPTED MANUSCRIPT
Ms (emu/g)
30
(a)
25 20 15 10 0.02
0.04
(b)
4.0 3.5 3.0 2.5 2.0
1.2
0.00
0.02
0.04
1.0 0.8 0.6 0.4 350
0.00
0.08
0.06
0.08
M AN U
(c) nB (µB)
0.06
0.02
0.04
0.10
RI PT
0.00
SC
Mr (emu/g)
4.5
0.10
0.06
0.08
0.10
0.06
0.08
0.10
0.06
0.08
0.10
300
TE D
Hc (Oe)
(d)
250 200
0.00
0.02
SQR
EP
0.30
0.04
(e)
0.25
AC C
0.20 0.15
0.00
0.02
0.04
Tb content (x)
Figure 8. Evolutions of (a) Ms, (b) Mr, (c) substitution content.
3+
, (d) Hc and (e) SQR with respect to Tb3+