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

Contents lists available at ScienceDirect

Ultrasonics - Sonochemistry journal homepage: www.elsevier.com/locate/ultson

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

T

Y. Slimania, , M.A. Almessierea,b, M. Sertkolc, Sagar E. Shirsathd, A. Baykale, M. Nawaze, S. Akhtara, B. Ozcelikf, I. Ercana ⁎

a

Department of Biophysics, Institute for Research and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441 Dammam, Saudi Arabia Department of Physics, College of Science, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441 Dammam, Saudi Arabia c Deanship of Preparatory Year, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441 Dammam, Saudi Arabia d School of Materials Science and Engineering, University of New South Wales, Kensington, Sydney, NSW 2052, Australia e Department of Nanomedicine Research, Institute for Research and Medical Consultations (IRMC), Imam Abdulrahman Bin Faisal University, P.O. Box 1982, 31441 Dammam, Saudi Arabia f Department of Physics, Faculty of Science and Letters, Cukurova University, 01330 Balcali-Adana, Turkey b

ARTICLE INFO

ABSTRACT

Keywords: Soft ferrites Magnetic properties Ni-Cu-Zn spinel ferrites Optical properties Cation distribution

In this study, Tm3+ ion substituted NiCuZn nanospinel ferrites, Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10), have been synthesized sonochemically. The structural, spectroscopic, morphological, optic and magnetic investigation of the samples were done by X-ray powder diffractometry (XRD), Fourier transform infrared spectrophotometry (FT-IR), UV–Vis diffused reflectance (%DR) spectrophotometry, transmission and scanning electron microscopies (TEM and SEM) along with EDX, Vibrating sample magnetometry (VSM), respectively. The purity of prepared products were confirmed via XRD, FT-IR, EDX and elemental mapping analyses. The analyses of magnetization versus M(H) (applied magnetic field) were performed at 300 and 10 K. The following magnetic parameters like Ms (saturation magnetization), SQR = Mr/Ms (squareness ratio), nB ( magnetic moment), Hc (coercivity) and Mr (remanence) have been discussed. M(H) loops revealed superparamagnetic property at RT and soft ferromagnetic nature at 10 K. It is showed that the Tm3+ substitutions significantly affect the magnetizations data. A decreasing trend in the Ms, Hc, Mr, and nB values was detected with Tm3+ substitution.

1. Introduction Spinel ferrites (MFe2O4 where M is Ni, Cu, Zn, Co, …) are interesting magnetic materials because of their high saturation magnetization (Ms), mechanical strength, chemical stability, high Curie temperature and high electromagnetic performance that could be altered either by changing the preparation method or doping it with a suitable element [1–4]. Nanosized spinel ferrites are used in several area including environment, biomedicine, energy, etc [5–9]. Owing to their high resistivity, chemical robustness/stability, low eddy current losses and low cost, Ni-Cu-Zn ferrites are used in multiplayer chip inductor applications [10]. Rare Earth (RE) doped NiCuZn ferrite can be also

⁎

used in magnetic storage devices, inductors, possessing good electromagnetic properties in the frequency region of radio waves, transformers, deflection yokes, multilayer electromagnetic interference filter (EMIF), recording heads, etc [11–15]. NiCuZn ferrite nanopowders and polycrystalline bulk samples were prepared by wet chemical (citrate) method followed by sintering step by Dimri et al. [11]. They showed that composite thick films exhibit lower dielectric and magnetic losses. Besides, the permeability and permittivity can be tailored for applications as microwave absorbers by varying the ferrite to polymer ratio in composite thick films. The resulting materials are suggested to be suitable for Microchips having multilayer chip inductors (MLCIs) operable in the low frequency range and even in high frequency devices and

Corresponding author. E-mail address: [email protected] (Y. Slimani).

https://doi.org/10.1016/j.ultsonch.2019.05.001 Received 4 April 2019; Received in revised form 1 May 2019; Accepted 2 May 2019 Available online 03 May 2019 1350-4177/ © 2019 Elsevier B.V. All rights reserved.

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

x=0.10

(440)

(422) (511)

(400)

(311)

x=0.10

(222)

(220)

Yobs Ycalc Bragg Pos.

x=0.08 % Transmittance (a.u.)

Intensity (a. u.)

x=0.08 x=0.06 x=0.04 x=0.02 x=0.00 20

30

40

50 2θ (°)

60

x=0.06

x=0.04

x=0.02

70 x=0.00

Fig. 1. XRD powder patterns of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites.

1200

Table 1 The structural parameters for Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites. x

a (Å)

V (Å)3

DXRD (nm) ± 0.05

χ2 (chi2)

RBragg

0.00 0.02 0.04 0.06 0.08 0.10

8.406(9) 8.407(3) 8.420(3) 8.421(5) 8.423(5) 8.427(6)

594.17 594.26 597.02 597.26 598.31 598.56

9.51 9.53 9.87 9.76 10.14 10.46

1.36 1.12 1.20 1.08 1.11 1.21

2.73 4.72 2.24 3.34 2.11 3.74

Tetrahedral A-site

Octahedral B-site

x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10

Zn0.4Ni0.05Fe0.55 Zn0.4Ni0.05Fe0.55 Zn0.4Ni0.05Fe0.55 Zn0.4Ni0.05Fe0.55 Zn0.4Ni0.06Fe0.54 Zn0.4Ni0.07Fe0.53

Ni0.25Cu0.3Fe1.45 Ni0.25Cu0.3Tm0.02Fe1.43 Ni0.25Cu0.3Tm0.04Fe1.41 Ni0.25Cu0.3Tm0.06Fe1.39 Ni0.24Cu0.3Tm0.08Fe1.38 Ni0.23Cu0.3Tm0.1Fe1.37

800

600

400

-1

Wavenumber (cm ) Fig. 2. FT-IR spectra of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites.

the Cu0.5−xNixZn0.5Fe2O4 NPs through the citrate precursor method and investigated their microwave absorption properties. The magnetic measurements showed that the NPs exhibit high saturation magnetization and low coercivity. Reflectivity measurements were found to be about 96.6% of radiation absorption in the nanopowders with Cu content of × = 0.2 at 12 GHz. The obtained results indicated that Cu additions resulted in very promising material that can be used in Radar absorption material. Kaiser et al. [16] investigated the Mossbauer and dielectric properties NixCu0.8−xZn0.2Fe2O4 compound. The physical properties of NiCuZn ferrite can be altered and tailored by substitutions with rare earth (RE) such as Eu3+, Sm3+, Gd3+, Pr3+, Dy3+, etc [17,18]. The difference in ionic radius between RE3+ and Fe3+ creates a deformation in the structure of spinel ferrites [18–20]. The 4f shells of RE3+ are essentially shielded by 5s25p6 sub-shells and the electrons are still unaltered by electric potential of neighboring ions [21,22]. Harzali et al. [17] investigated the structural, magnetic and optical properties of nanosized Ni0.4Cu0.2Zn0.4R0.05Fe1.95O4 (R = Eu3+, Sm3+, Gd3+ and Pr3+) ferrites synthesized by co-precipitation method with ultrasound irradiation. The experimental results showed that coprecipitation method coupled with ultrasound irradiation can lower the crystallite size and favors in getting a single spinel phase. The saturation magnetization (Ms) measured using VSM at room temperature increases with increasing ionic radius (Eu3+ ≥ Gd3+ > Sm3+ > Pr3+). Varalaxmi et al. [23] reported the structural and dielectric studies of magnesium substituted NiCuZn ferrites for microinductor applications. Kabbur et al. [24] reported the magnetic and electrical properties of Tb3+ doped NiCuZn ferrite NPs. Samples were synthesized by glycine assisted autocombustion route. They showed that the present Tb3+

Table 2 Cation distribution of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites. Composition

1000

components. Nakamura [12] reported the successful synthesis of Ni-CuZn spinel ferrites with high density, high permeability and high Ms using the usual ceramic technique. It was reported that the used synthesis condition in this study is suitable for producing multilayer chip inductors. Nanocrystalline Ni-Cu-Zn ferrites were synthesized through a sol–gel method using gelatin by Gabal et al. [13]. Also, Gabal [14] synthesized the Ni-Cu-Zn spinel ferrites using egg-white. Hysteresis loops measurements showed an increase in the Ms value with zinc content (Ni0.8−xCu0.2ZnxFe2O4) up to 0.2%. Lima et al. [15] prepared

204

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

Fig. 3. SEM images of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.00, 0.02, 0.06 and 0.10) nanospinel ferrites.

substituted NiCuZn ferrite systems with soft magnetic properties, moderate electrical resistivity, high permeability and low dielectric loss at high frequency are potential candidate for MLCI component applications. In another study, Shirsath et al. [25] synthesized Dy3+ doped NiCuZn ferrites by sol–gel auto-combustion method and they disclosed and enhancement in magnetic properties. Sol–gel synthesis method (flash-combustion method, auto-ignition or self-propagation, low-temperature self-combustion, etc.) is the mixture of chemical sol–gel and combustion procedure. The large mass loss throughout the xerogel combustion following by rapid evaluation of gases results in the formation of ferrite nanopowders [26]. It has many advantages over other synthesis routes like high product purity and crystallinity, low processing time, good chemical homogeneity etc. [26]. In the literature, no report on the sonochemical synthesis and characterization of Tm3+ substituted NiCuZn spinel ferrites. Therefore, we aim in the present work to synthesize nano-sized Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) spinel ferrites through ultrasound irradiation and evaluate their structural, cation distribution, magnetic, optical properties.

reaction temperature was measured as 85 °C. The final solid product was cleaned with DI water. It was dried at 70 °C. Rigaku Benchtop Miniflex XRD (Bruker FT-IR) with CuKα radiation, FEI Morgagni 268 TEM, FEI SEM, Quantum Design SQUID were used for structural, spectroscopic, morphological and magnetic investigation, respectively. 3. Results and discussion 3.1. XRD examination XRD powder patterns of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites are presented in Fig. 1, which have good agreement with the JCPDS card no. 39-1277 of NiFe2O4. The purity and cell parameters of prepared samples were verified and determined by Rietveld analysis (Table 1). No secondary phase was detected. In the literature, it was well-established that the RE3+ ions favorably occupy the octahedral site as a result of their large ionic radii [27,28]. It was pointed out that the lattice constant (a) is increasing with increasing Tm3+ concentration, mostly owing to the greater ionic radius of Tm3+ ions (0.88 Å) than that to Fe3+ (0.645 Å). The crystallites size (DXRD) increases with the rise in Tm3+ content [27]. The observed result is well in compliance with that observed in Tb–Dy substituted Li-Ni nanoferrites [29]. In this study, the solubility limit was not determined. The site occupancy of cations in the Ni0.3Cu0.3Zn0.4TmxFe2−xO4 ferrite system was performed by analyzing XRD patterns. The cation distribution was calculated via Bertaut method [29]. These XRD lines of I220/I440 and I422/I400 are presumed to be sensitive to the cation distribution. Thus, the ratio of these lines is utilized to deduce the distribution of divalent and trivalent cations amongst the A and B sites in all products. It should be noted that the factors of absorption and temperature do not alter the intensity calculation, so these factors are not considered in our calculations [31]. The cations distribution results for Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites are

2. Experimental The series of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites were produced sonochemically. All chemicals (Ni (NO3)2·6H2O, Cu(NO3)2·3H2O, Zn(NO3)2·6H2O, Fe(NO3)3·9H2O, Tm2O3, C2H5OH, NH3 were obtained from US Research Nanomaterials and Merck, Inc. The specific contents of various nitrates were dissolved in deionized water (DI H2O) and Tm2O3 was dissolved in 10 ml HCl. Next, metal nitrate solutions were mixed. After that, the pH was arranged to 11 by NH3 solution. Then, mixture was subjected to ultrasonic irradiation with high-intensity (UZ SONOPULS HD 2070 Ultrasonic homogenizer) for 30 min. During ultrasonication, there will be great number of collisions among the reactants and hence the

205

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

Fig. 4. EDX and elemental mapping of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.04 and 0.08) nanospinel ferrites.

shown in Table 2. It is noted that the cations display closely linear composition and substitution dependencies. Since Tm is substituted for Fe3+ ions, the percentage of the Fe ions at A and B sites decreased. It is well-known that Ni and Cu ions have preference to occupy the octahedral site, which is true in the present case however small percentage of Ni ions migrated from octahedral site to tetrahedral site. This could be due to the more competition of majority of ions to occupy octahedral

site. Tm ions as expected occupy octahedral site because of their larger ionic radii that cannot be accommodated in tetrahedral site. Zn and Cu ions only occupy tetrahedral and octahedral sites respectively. 3.2. FT-IR analysis The FT-IR spectra of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10)

206

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

x=0.04

x=0.04

50

x=0.04

Count (%)

40 30 20 10 0

100 nm

5

10

15

20

25

20

25

Size (nm)

x=0.08

50 220

311 400

511

x=0.08

40

Count (%)

x=0.08

440

100 nm

30 20 10 0 5

10

15

Size (nm)

DR (%)

Fig. 5. TEM image, selected area electron diffraction pattern and size histogram of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.04 and 0.08) nanospinel ferrites.

200

mapping are employed as seen in Fig. 4. It was found that the Ni, Cu, Zn, Tm, Fe and O are presence. Fig. 5 displays the TEM images of the Tm substituted Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.04 and 0.08) nanospinel ferrites. The particles were cubical in structure and appeared in agglomeration due to their magnetic nature. The histograms depict the size distribution of the particles, the average size is found nearly the same for both the specimens. The particle size estimated by TEM is comparable with the DXRD value found by XRD. The nanoparticles exhibited wellseparated continuous rings when analyzed by electron diffraction, SAED. The first five rings of the SAED patterns were identified as, (2 2 0), (3 1 1), (4 0 0), (5 1 1) and (4 4 0). The maximum diffraction intensity was found for (3 1 1) plan, consistent with the XRD pattern as shown by Fig. 1.

X = 0.00 X = 0.02 X = 0.04 X = 0.06 X = 0.08 X = 0.1

300

400

500

600

Wavelength (nm)

700

800

Fig. 6. DR % spectra of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites performed in the near UV and visible region.

3.4. Optic study UV–visible %DR is important technique to study the optical properties of nanomaterial. UV–visible %DR spectra of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites were obtained (Fig. 6). The spectra clearly indicated that Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites exhibited absorption in the visible range. Kubelka-Munk model is widely used to estimate the band gap energy (Eg) of nanomaterials and in our study this model was also used [35–38]. Plots of (αhv)2 vs. photon energy (hv) were done to estimate the Eg of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites (Fig. 7). The band gap of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites at different concentrations is shown in the Fig. 7. The results clearly indicate that upon increasing × concentration the band gap value is increased overall. Similar trend was observed in other spinel ferrite systems [39]. The increase in band gap might be attributed to the interface defects or the development of energy level in Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites [40]. Furthermore, the synergistic effect in Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites is also responsible for

nanospinel ferrites were depicted in Fig. 2. All ratios showed identical spectra with strong absorption bands at 570 and 410 cm−1. These two bands are the characteristic stretching vibrations of spinel ferrites which can be identified as ν1 and v2 for A and B sites, respectively [32–34]. In spinel ferrites Zn2+ and Ni2+ ions have stronger preference to reside in A and B sites respectively. Ions of Cu2+ and Fe3+ could be at the both sites even though they prefer the B site, while Tm3+ ions occupied the B site only [20,23,32]. 3.3. SEM/TEM, EDX and elemental mapping Fig. 3 denoted SEM images of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.00, 0.02, 0.06 and 0.10) nanospinel ferrites. The samples exhibited a crystalline shape of agglomeration of small particles. To confirm the stoichiometric of the elements that the Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (x = 0.00, 0.02, 0.06 and 0.08) are consisted, EDX and elemental

207

Ultrasonics - Sonochemistry 57 (2019) 203–211

-1 2

Y. Slimani, et al.

-1 2

X = 0.02 Eg = 1.80 eV

( hv) [eV-cm ]

(

2

2

hv) [eV-cm ]

X = 0.00 Eg = 1.78 eV

0

2

4

6

hv (eV)

0

( hv) [eV-cm ]

-1 2

X = 0.04

( hv) [eV-cm ]

3

4

5

6

3

4

5

6

3

4

hv (eV)

2

2

2

X = 0.06 Eg = 1.89 eV

-1 2

Eg = 1.80 eV

1

1

2

3

4

hv (eV)

5

6

1

2

hv (eV)

X = 0.1 Eg = 1.94 eV

2

2

( hv) [eV-cm ]

X = 0.08 Eg = 1.90 eV

( hv) [eV-cm ]

0

-1 2

-1 2

0

0

1

2

3

4

hv (eV)

5

6

0

1

2

hv (eV)

5

6

Fig. 7. Tauc plots of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites samples. Extrapolation of straight portion of graph to energy axis at the ( h )2 = 0 gives the Eg value.

the increased band gap value of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites [40].

The considered Mr and Hc values of various products are negligible at RT. According to the mentioned characteristics of magnetic data, one can affirm that the different produced Ni0.3Cu0.3Zn0.4TmxFe2−xO4 NPs present superparamagnetic (SPM) nature at RT. However, at low temperatures, Mr and Hc values are in the range of 6.4–10.3 emu/g and 108.0–169.6 Oe, respectively. Therefore, the various produced Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites present soft ferromagnetic (FM) nature at 10 K. Furthermore, one should note that the various magnetic parameters are increased at low temperature compared to RT. This is largely attributable to a reduction of thermal fluctuations of magnetic moments at lower temperatures [44,45]. The impacts of Tm3+ substitution on the Ms, Mr and Hc of prepared Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites were evaluated. The pristine Ni0.3Cu0.3Zn0.4Fe2O4 (x = 0.00) nanospinel ferrite exhibits Ms

3.5. Magnetization analyses The M(H) hysteresis loops for all Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.00 ≤ x ≤ 0.10) nanospinel ferrites were performed at RT and 10 K and are illustrated in Fig. 8. Obviously, Tm3+ substitutions in Fe3+ sites affect significantly the magnetic properties of Ni0.3Cu0.3Zn0.4Fe2O4 spinel ferrite. In order to extract the Ms values, the Stoner–Wohlfarth (S–W) approach was utilized as reported in the references [41–43]. The various NPs exhibit Ms magnitudes in the range 15.9–35.8 and 42.7–68.0 emu/g at RT and 10 K, respectively. Mr and Hc values at RT are in the interval of 0.29–0.64 emu/g and 12.5–13.1 Oe, respectively.

208

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

40 30

(a)

x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10

20

M (emu/g)

a decrease in crystallites size. In other words, the reduction in DXRD is followed by a reduction in Ms and Mr magnitudes. Furthermore, we note that the Tm3+ ions radius (0.88 Å) are larger that of Fe3+ ions (0.645 Å). This contrast in ionic radii might cause strains that instigate variations of electronic states and disorder in ferrite systems [30,46]. In addition, the variations in nB could explain the variations in Ms magnitudes. The relation between nB and Ms is given by [30,46]:

T = 300 K

10 0

nB =

20

-10

10

The evolutions in nB values for all concentrations at RT and 10 K are presented in Fig. 9(e) and (f), respectively. Regularly, the decrease in nB values is originating from the weakening in the super-exchange interactions between various sites conducts to a decrement innB . In our case, the × = 0.00 sample present the greatest nB and Ms. With the increase in Tm3+ concentration, nB showed a decreasing tendency like that of Ms and Mr. These results imply a weakening of the super-exchange interactions with Tm3+ substitution content in Ni0.3Cu0.3Zn0.4TmxFe2−xO4 nanospinel ferrites. The evolutions of Hc values versus Tm3+ content showed that Hc reduces with Tm3+ substitution at both considered temperature (Fig. 9(g) and (h)). Generally, the coercivity is principally governed by numerous parameters including the magneto-crystalline anisotropy, morphology, shape and grains size [30,46,51,52]. The SQR values at RT and 10 K are also determined and presented in the Fig. 2(i) and (j). It is known that for cubic and uniaxial anisotropy, the SQRs are around 0.83 and 0.5, respectively [30,46]. Additionally, when the SQR is equal or greater than 0.5, the nanoparticles are in multi-magnetic domains (MD) [30,46]. However, if SQR is inferior than 0.5, the nanoparticles are generally considered to be in single magnetic domain (SD) [30,46]. According to the obtained SQR values, it can be concluded that all prepared products present SD nature with uniaxial anisotropy at RT and 10 K. We note that the prepared NPs display SQRs lower than 0.5 at both considered temperatures, which might be accredited to surface spin disorder effects [30,46].

0

-20

-10

-30 -40

60

-20 -1.0

-10

(b)

-0.5

0

0.0

0.5

5

H (kOe)

1.0

10

T = 10 K x = 0.00 x = 0.02 x = 0.04 x = 0.06 x = 0.08 x = 0.10

40

M (emu/g)

-5

20 0

40

-20

20 0

-40

-20

-60

-40 -1.0

-10

-5

0

H (kOe)

-0.5

0.0

5

0.5

Molecular Weight × Ms 5585

1.0

10

4. Conclusion

Fig. 8. Magnetization against applied magnetic field, M(H), performed at (a) 300 K and (b) 10 K of Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.00 ≤ x ≤ 0.10) NPs.

Ni0.3Cu0.3Zn0.4TmxFe2−xO4 (0.0 ≤ x ≤ 0.10) nanospinel ferrites were synthesized via cheap and environmentally friendly sonochemcial approach. The structure analyses via XRD revealed the successful formation of pure NiCuZn nanospinel ferrites without any impurity. The lattice constant is increased as a result of substitution of Fe3+ with Tm3+ having larger ions. The crystallites sizes (DXRD) are around 10 nm. The cation distribution calculations were also performed and confirmed the substitution of Tm3+ ion into NiCuZn spinel ferrites. SEM images showed a crystalline shape of agglomeration of small particles due to the magnetic interaction between magnetic nanoparticles. It is found that the Eg increased from 1.78 eV up to 1.94 eV with the increase in Tm3+ amount. This is mostly a result of the development of energy level or interface defects. M(H) analyses performed at RT and 10 K showed superparamagnetic and soft ferromagnetic behaviors, respectively. The pristine product exhibits the highest values of Ms (35.8 emu/ g at RT and 68.0 emu/g at 10 K), Mr (0.64 emu/g at RT and 10.3 emu/g at 10 K) and Hc (13.1 Oe at RT and 169.6 Oe at 10 K). The deduced Ms, Mr, Hc and nB magnitudes decreased with increasing the Tm3+ substitution content. The observed decline in Ms, Mr and Hc are a result of the creation of local strains, the weakening of super-exchange interactions, the decrease in grains size (or crystallites size) and the decreasing in the magnetic moments (nB ). The squareness ratio (SQR) are found to be lower than 0.5, which reveal the single magnetic domain nature in various produced Tm3+ substituted NiCuZn NPs.

values of about 35.8 and 68.0 emu/g at RT and 10 K, respectively. The obtained magnitudes are smaller than that for various bulk inverse spinel ferrites. The lower Ms compared to that of bulk material is largely accredited to the smaller crystallites size. This leads a structural disorder on the surface because the spins disorder will be significant when the volume and surface ratio is important [46,47]. The spins canting as a result of antiferromagnetic interactions competition and the disordered cations distribution on the surface could explain the lowering of Ms magnitude [47,48]. At both measured temperatures, the Ms values exhibited a decreasing tendency with increasing the Tm3+ substitution content in Ni0.3Cu0.3Zn0.4Fe2O4 nanospinel ferrite. Ms reached the minimum values for x = 0.10 product. Similar trend is being observed in Mr variations. Compared to × = 0.00 product, Mr showed a decreasing behavior with increasing Tm3+ content. In fact, the evolutions in Mr values follow principally the evolutions in Ms [49]. In the literature, several parameters could alter the magnetic properties of NPs such as strains, variations in grains size, strength of super-exchange interactions, variations in magnetic moments (nB ), etc. [49,50]. It is reported previously that Ms decreases with decreasing grains size [49,50]. The observed decreases in Ms and Mr magnitudes with increasing Tm3+ content is in conformity with XRD findings that showed

209

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al.

Fig. 9. Evolutions of (a, b) Ms, (c, d) Mr, (e, f) nB , (g, h) Hc and (i, j) SQR with respect to Tm3+ substitution content at both RT (Right) and 10 K (Left).

Acknowledgments

catalysts, J. Nanosci. Nanotechnol. 16 (2016) 7325–7336. [4] Y. Slimani, M.A. Almessiere, S. Güner, N.A. Tashkandi, A. Baykal, M.F. Sarac, M. Nawaz, I. Ercan, Calcination effect on the magneto-optical properties of vanadium substituted NiFe2O4 nanoferrites, J. Mater. Sci.: Mater. Electron. (2019), https://doi.org/10.1007/s10854-019-01243-x. [5] H. Tombuloglu, Y. Slimani, G. Tombuloglu, M. Almessiere, A. Baykal, I. Ercan, H. Sozeri, Tracking of NiFe2O4 nanoparticles in barley (Hordeum vulgare L.) and their impact on plant growth, biomass, pigmentation, catalase activity, and mineral uptake, Environ. Nanotechnol. Monit. Manage. 11 (2019) 100223. [6] H. Tombuloglu, G. Tombuloglu, Y. Slimani, I. Ercan, H. Sozeri, A. Baykal, Impact of manganese ferrite (MnFe2O4) nanoparticles on growth and magnetic character of barley (Hordeum vulgare L), Environ. Pollut. 243 (2018) 872–881. [7] M. Nawaz, Y. Sliman, I. Ercan, M.K. Lima-Tenório, E.T. Tenório-Neto, C. Kaewsaneha, A. Elaissari, Magnetic and pH-responsive magnetic nanocarriers, Stimuli Responsive Polymeric Nanocarriers for Drug Delivery Applications, Woodhead Publishing, 2019, pp. 37–85. [8] M.K. Ben Salem, Y. Slimani, E. Hannachi, F. Ben Azzouz, M. Ben Salem, Bi-based superconductors prepared with addition of CoFe2O4 for the design of a magnetic probe, Cryogenics 89 (2018) 53–57. [9] Y. Slimani, E. Hannachi, F. Ben Azzouz, M. Ben Salem, Comparative study of the effect of magnetic nanoparticle CoFe2O4 on fluctuation-induced conductivity of Y123 and Y-358 superconductors, J. Supercond. Nov. Magn. 32 (2019) 511–519.

The authors appreciate the support of the Institute for Research & Medical Consultations (Projects No. 2019-IRMC-S-1, No. 2018-IRMC-S2 and No. 2017-IRMC-S-3) and Deanship for Scientific Research (Project No. 2018-209-IRMC) of Imam Abdulrahman Bin Faisal University (IAU – Saudi Arabia). References [1] S.E. Shirsath, D. Wang, S.S. Jadhav, M.L. Mane, S. Li, Ferrites obtained by sol-gel method, in: L. Klein, M. Aparicio, A. Jitianu (Eds.), Handbook of Sol-Gel Science and Technology, Springer, Cham, 2018, pp. 695–735. [2] A. Manikandan, M. Durka, M. Amutha Selvi, S. Arul Antony, Sesamum indicum Plant extracted microwave combustion synthesis and opto-magnetic properties of spinel MnxCo1−xAl2O4 nano-catalysts, J. Nanosci. Nanotechnol. 16 (2016) 448–456. [3] E. Hema, A. Manikandan, P. Karthika, M. Durka, S. Arul Antony, B.R. Venkatraman, Magneto-optical properties of reusable spinel NixMg1−xFe2O4 (0.0≤ x≤ 1.0) nano-

210

Ultrasonics - Sonochemistry 57 (2019) 203–211

Y. Slimani, et al. [10] Sagar E. Shirsath, S.S. Jadhav, M.L. Mane, S. Li, Ferrites obtained by Sol–Gel method, in: L. Klein, M. Aparicio, A. Jitianu (Eds.), Handbook of Sol-Gel Science and Technology, Springer, Cham, 2018. [11] C. Mukesh Dimri, C. Subhash Kashyap, D.C. Dube, High frequency behaviour of low temperature sintered polycrystalline NiCuZn ferrites and their composite thick films, Phys. Status Solidi A 207 (2) (2010) 396–400. [12] T. Nakamura, Low-temperature sintering of Ni-Zn-Cu ferrite and its permeability spectra, J. Magn. Magn. Mater. 168 (1997) 285–291. [13] M.A. Gabal, Y.M. Al Angari, A.Y. Obaid, A. Qusti, Structural analysis and magnetic properties of nanocrystalline NiCuZn ferrites synthesized via a novel gelatin method, Adv. Powder Technol. 25 (2014) 457–461. [14] M.A. Gabal, Magnetic properties of NiCuZn ferrite nanoparticles synthesized using egg-white, Mater. Res. Bull. 45 (2010) 589–593. [15] U.R. Lima, M.C. Nasar, R.S. Nasar, M.C. Rezende, J.H. Aråjo, J.F. Oliveira, Synthesis of NiCuZn ferrite nanoparticles and microwave absorption characterization, Mater. Sci. Eng., B 151 (2008) 238–242. [16] M. Kaiser, S.S. Ata-Allah, Mossbauer effect and dielectric behavior of NixCu0.8−xZn0.2Fe2O4 compound, Mater. Res. Bull. 44 (2009) 1249–1255. [17] H. Harzali, A. Marzouki, F. Saida, A. Megriche, A. Mgaidi, Structural, magnetic and optical properties of nanosized Ni0.4Cu0.2Zn0.4R0.05Fe1.95O4 (R = Eu3+, Sm3+, Gd3+ and Pr3+) ferrites synthesized by co-precipitation method with ultrasound irradiation, J. Magn. Magn. Mater. 460 (2018) 89–94. [18] S.E. Shirsath, R.H. Kadam, S.M. Patange, M.L. Mane, A. Ghasemi, A. Morisako, Enhanced magnetic properties of Dy3+ substituted Ni-Cu-Zn ferrite nanoparticles, Appl. Phys. Lett. 100 (4) (2012) 042407. [19] X. Wu, Z. Ding, N. Song, L. Li, Effect of the rare-earth substitution on the structural, magnetic and adsorption properties in cobalt ferrite nanoparticles, Cer. Int. 42 (2015) 160. [20] K. Elayakumar, A. Manikandan, A. Dinesh, K. Thanrasu, K. Kanmani Raja, R. Thilak Kumar, Y. Slimani, S.K. Jaganathan, A. Baykal, Enhanced magnetic property and antibacterial biomedical activity of Ce3+ doped CuFe2O4 spinel nanoparticles synthesized by sol-gel method, J. Magn. Magn. Mater. 478 (2019) 140–147. [21] 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. [22] M. Maria Lumina Sonia, S. Anand, V. Maria Vinosel, M. Asisi Janifer, S. Pauline, A. Manikandan, Effect of lattice strain on structure, morphology and magneto-dielectric properties of spinel NiGdxFe2−xO4 ferrite nano-crystallites synthesized by sol-gel route, J. Magn. Magn. Mater. 466 (2018) 238–251. [23] N. Varalaxmi, K.V. Sivakumar, Structural and dielectric studies of magnesium substituted NiCuZn ferrites for microinductor applications, Mater. Sci. Eng. 184 (2014) 88–97. [24] S.M. Kabbur, U.R. Ghodake, R.C. Kambale, S.D. Sartale, L.P. Chikhale, S.S. Suryavanshi, Magnetic, electric and optical properties of Mg-substituted Ni-CuZn ferrites, J. Elect. Mater. 46 (2017) 5693. [25] S.E. Shirsath, R.H. Kadam, S.M. Patange, M.L. Mane, A. Ghasemi, A. Morisako, Appl. Phys. Lett. 100 (4) (2012) 042407. [26] A. Sutka, G. Mezinskis, Sol–gel auto-combustion synthesis of spinel-type ferrite nanomaterials, Front. Mater. Sci. 6 (2) (2012) 128–141. [27] M.A. Khan, M. Sabir, A. Mahmood, M. Asghar, K. Mahmood, M.A. Khan, I. Ahmad, M. Sher, M.F. Warsi, High frequency dielectric response and magnetic studies of Zn1−xTbxFe2O4 nanocrystalline ferrites synthesized via micro-emulsion technique, J. Magn. Magn. Mater. 360 (2014) 188–192. [28] M. Ishaque, M.U. Islam, M. Azhar Khan, I.Z. Rahman, A. Genson, S. Hampshire, Structural, electrical and dielectric properties of yttrium substituted nickel ferrites, Phys. B Condens. Matter. 405 (2010) 1532–1540. [29] M. Junaid, M.A. Khan, F. Iqbal, G. Murtaza, M.N. Akhtar, M. Ahmad, I. Shakir, M.F. Warsi, Structural, spectral, dielectric and magnetic properties of Tb–Dy doped Li-Ni nano-ferrites synthesized via micro-emulsion route, J. Magn. Magn. Mater. 419 (2016) 338–344. [30] S.E. Shirsath, M.L. Mane, Y. Yasukawa, X. Liu, A. Morisako, Chemical tuning of structure formation and combustion process in CoDy0.1Fe1.9O4 nanoparticles: influence@pH, J. Nanopart. Res. 15 (2013) 1976. [31] S.E. Shirsath, M.L. Mane, Y. Yasukawa, X. Liu, A. Morisakoa, Self-ignited high temperature synthesis and enhanced super-exchange interactions of Ho3+–Mn2+–Fe3+–O2− ferromagnetic nanoparticles, PCCP 16 (2014) 2347–2357. [32] M.A. Almessiere, Y. Slimani, A.D. Korkmaz, S. Guner, M. Sertkol, Sagar E. Shirsath, A. Baykal, Structural, optical and magnetic properties of Tm3+ substituted cobalt spinel ferrites synthesized via sonochemical approach, Ultrason. – Sonochem. 54 (2019) 1–10.

[33] A. Manikandan, E. Hema, M. Durka, K. Seevakan, T. Alagesan, S. Arul Antony, Room temperature ferromagnetism of magnetically recyclable photocatalyst of Cu1−xMnxFe2O4-TiO2 (0.0≤ x≤ 0.5) nanocomposites, J. Supercond. Nov Magn. 28 (2015) 1783–1795. [34] G. Padmapriya, A. Manikandan, V. Krishnasamy, Saravana Kumar Jaganathan, S. Arul Antony, Spinel NixZn1−xFe2O4 (0.0≤ x≤ 1.0) nano-photocatalysts: synthesis, characterization and photocatalytic degradation of methylene blue dye, J. Mol. Struct. 1119 (2016) 39–47. [35] A.D. Korkmaz, S. Güner, Y. Slimani, H. Gungunes, Md. Amir, A. Manikandan, A. Baykal, Microstructural, optical, and magnetic properties of vanadium-substituted nickel spinel nanoferrites, J. Supercond. Nov. Magn. (2018), https://doi. org/10.1007/s10948-018-4793-6. [36] A. Manikandan, E. Manikandan, B. Meenatchi, S. Vadivel, S.K. Jaganathan, R. Ladchumananandasivam, M. Henini, M. Maaza, Jagathrakshakan Sundeep Aanand, Rare earth element (REE) lanthanum doped zinc oxide (La: ZnO) nanomaterials: synthesis structural optical and antibacterial studies, J. Alloy. Compd. 723 (2017) 1155–1161. [37] Y. Slimani, B. Unal, E. Hannachi, A. Selmi, M.A. Almessiere, M. Nawaz, A. Baykal, I. Ercan, M. Yildiz, Frequency and dc bias voltage dependent dielectric properties and electrical conductivity of BaTiO3SrTiO3/(SiO2)x nanocomposites, Ceram. Int. 45 (2019) 11989–12000. [38] Y. Slimani, A. Selmi, E. Hannachi, M.A. Almessiere, A. Baykal, I. Ercan, Impact of ZnO addition on structural, morphological, optical, dielectric and electrical performances of BaTiO3 ceramics, J. Mater. Sci.: Mater. Electron. (2019), https://doi. org/10.1007/s10854-019-01284-2. [39] A. Manikandan, M. Durka, S. Arul Antony, A novel synthesis, structural, morphological, and opto-magnetic characterizations of magnetically separable spinel CoxMn1−xFe2O4 (0≤ x≤ 1) Nano-catalysts, J. Supercond. Nov Magn. 27 (2014) 2841–2857. [40] S. Güner, A. Baykal, Md. Amir, H. Güngüneş, M. Geleri, H. Sözeri, Sagar E. Shirsath, M. Sertkol, Synthesis and characterization of oleylamine capped MnxFe1−xFe2O4 nanocomposite: magneto-optical properties, cation distribution and hyperfine interactions, J. Alloy. Compd. 888 (2016) 675–686. [41] X. Li, Y. Hou, Q. Zhao, L. Wang, A general, one-step and template-free synthesis of sphere-like zinc ferrite nanostructures with enhanced photocatalytic activity for dye degradation, J. Colloid Interface Sci. 358 (2011) 102. [42] E.C. Stoner, E. Wohlfarth, A mechanism of magnetic hysteresis in heterogeneous alloys, Philos. Trans. R. Soc. London Ser. A Math. Phys. Sci. 240 (1948) 599–642. [43] M.A. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Morphology and magnetic traits of strontium nanohexaferrites: effects of manganese/yttrium co-substitution, J. Rare Earths (2019), https://doi.org/10.1016/j.jre.2018.09.014. [44] M. Almessiere, Y. Slimani, H.S. El Sayed, A. Baykal, Ca2+ and Mg2+ incorporated barium hexaferrites: structural and magnetic properties, J. Sol-Gel Sci. Technol. 88 (2018) 628–638. [45] 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. [46] 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 Phys. 13 (2019) 102166. [47] 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. [48] M. Almessiere, A.D. Korkmaz, Y. Slimani, M. Nawaz, S. Ali, A. Baykal, Magnetooptical properties of rare earth metals substituted Co-Zn spinel nanoferrites, Ceram. Int. 45 (2019) 3449–3458. [49] M. Amir, H. Gungunes, Y. Slimani, N. Tashkandi, H. El Sayed, F. Aldakheel, M. Sertkol, H. Sozeri, A. Manikandan, I. Ercan, Mössbauer studies and magnetic properties of cubic CuFe2O4 nanoparticles, J. Supercond. Nov Magn. 32 (2019) 557–564. [50] M. Almessiere, Y. Slimani, S. Güner, A. Baykal, I. Ercan, Effect of dysprosium substitution on magnetic and structural properties of NiFe2O4nanoparticles, J. Rare Earths (2019), https://doi.org/10.1016/j.jre.2018.10.009. [51] 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. [52] M.A. Almessiere, Y. Slimani, S. Ali, A. Baykal, I. Ercan, H. Sozeri, Nd3+ ion-substituted Co1−2xNixMnxFe2−yNdyO4 nanoparticles: structural, morphological, and magnetic investigations, J. Inorg. Organomet. Polym. 29 (2019) 783–791.

211