Synthesis, Properties, and Applications of Multifunctional Magnetic Nanostructures 2018
View this Special IssueResearch Article  Open Access
Investigation of the Magnetic Properties of Ferrites in the CoONiOZnO Using SimplexLattice Design
Abstract
The article is devoted to the analysis of changes in the magnetic characteristics of ferrites in the CoONiOZnO system by the simplex method. Ferrites of NiZn, CoZn, and CoNi were synthesized in the form of nanoparticles (2040 nm) using a new method for processing contact nonequilibrium lowtemperature plasma (CNP). The effect of the mutual influence of the contents of different cations on the saturation magnetization and the coercive field was investigated using the simplexlattice method. A magnetic investigation using a vibrational magnetometer shows that low magnetization values are observed for NiZn ferrites and high for the entire CoZn and CoNi ferrite series. EPR spectra show that the value of the resonant field and line width corresponds to the value of magnetic saturation and is due to the arrangement of cations on sublattices.
1. Introduction
Oxides of composition MeFe_{2}O_{4} (MeNi^{2+}, Co^{2+}, Zn^{2+}) have important technological properties. For example, ferrites of transition metals with a spinel structure are used as magnetic electrical materials [1, 2] catalysts of a number of reactions [3, 4]. Technological operations for the synthesis of such compounds require, as a rule, the use of hightemperature heat treatment and complex hardware. In this case, both traditional ceramic (from metal oxides) methods and novel technologies are used. For example, in the synthesis of nickel (II) ferrite, cobalt (II) and zinc (II), and hydrothermal methods [5], microwave treatment [6] is used. The attention of chemists is concentrated on the development of new methods for obtaining ferrites of transition materials with a given set of properties. A characteristic trend of recent times is the development of technologies for obtaining nanodispersed ferrites.
It is known that nanosized spinel ferrites exhibit properties and phenomena that cannot be explained on the basis of the structure and properties of the consolidated substance [1, 2]. Thus, the transition of ferrites of transition metals to a nanoscale state is accompanied by a significant change in their magnetic properties (coercive field, magnetization magnitudes, crystallographic anisotropy, and Curie temperature). And their properties essentially depend on the technology of obtaining samples. The authors of [7] point out that the effect of size effects in the synthesis of nanoscale ferrospinels by coprecipitation of salt solutions with the use of additional highenergy shortterm exposures is much stronger than in the case of using traditional technologies. The creation of adequate models of the magnetic state of such materials is one of the urgent problems of materials science. This is due both to the wide possibilities of their practical use and to the need to develop theoretical ideas about the effect of dimensional and surface effects on magnetic properties [8, 9]. There is no unified theory that explains the variation of magnetic properties over a wide range. At present, there are basic theories. The “shell” model gives a qualitative explanation of the effect of decreasing magnetization with decreasing particle sizes. Neel’s theory establishes the dependence of the magnetization on the distribution of cations over the sublattices. A theory is known [10] about the formation of the magnetic properties of nanosized ferrimagnets due to the anisotropy induced by internal elastic microstrains.
The aim of this work is to establish the relationship between the magnetic characteristics of ferrites of the composition MeFe_{2}O_{4} (MeNi, Co, Zn) and structural characteristics obtained by processing a contact nonequilibrium lowtemperature plasma.
2. Materials and Methods
In order to reduce energy consumption, temperature, and time of synthesis in the production of ferrites of different composition, in this work, a method of precipitation of hydroxides was used, followed by treatment of the suspension with CNP, washing, and drying.
Reagent grade FeSO_{4}^{⋅}7H_{2}O, NiSO_{4}^{⋅}7H_{2}O, CoSO_{4}^{⋅}7H_{2}O, and ZnSO_{4}^{⋅}7H_{2}O were used as the starting materials.
The hydroxide sol which was obtained by alkali precipitation was treated with contact lowtemperature nonequilibrium plasma in a laboratory plasma chemical plant, which consists of a singlestage plasma reactor of a discrete type, a stepup transformer, an ignition transformer, and a vacuum pump. After treatment, the resulting precipitate was washed and dried for further investigation. Plasmachemical treatment of suspensions was carried out in a gasliquid plasmachemical reactor of periodic action. The reactor is made of glass and is equipped with an external jacket for thermostating the medium to be treated. Electrodes of stainless steel are placed in the lower and upper part of the reactor. 40 cm^{3} of slurry was poured into the reactor; the anode position was adjusted so that the distance between its lower base and the surface of the liquid was 10.0 mm. The plasma column formed as a result of breakdown was a tool for processing. To obtain a plasma discharge, the pressure in the reactor was maintained at 0.08 MPa. Electrodes were supplied with a direct current with a voltage in the range of 500600 V, the value of which was varied so that the current strength in the circuit was 100150 mA.
Xray diffraction patterns of the pigments were obtained on a DRON2.0 instrument in monochromatized Co_{α} radiation. The lattice parameter was calculated from the SelyakovScherrer equation.
The determination of the magnetic characteristics was carried out using a vibration magnetometer. A change in the solution medium was observed at regular intervals using a pH meterpH150 MI. EPR spectra were obtained using a Radiopan SE/X2543 radio spectrometer. The signal strength, the resonant magnetic field, and the signal width were used to characterize the ESR signals.
Simplexlattice design was used to study the effect of the composition on the properties of ferrites, requiring a minimum number of experiments to study the influence of factors on the selected response functions [11]. The molar concentrations of cobalt, nickel, and zinc cations, respectively, were chosen as factors x_{1}, x_{2}, and x_{3}. The design of the experiment is shown in Table 1.

The upper and lower limits of each component were distributed as follows:
Iron cation content is 0.67 (%). Three components of the model recipes changed simultaneously.
When studying the properties of a mixture, depending on the content of the components in it, the factor space can be represented as a regular simplex. An example of a simplex in twodimensional space is a regular triangle.
For mixtures, the following relation holds: where x_{i} ≥ 0 is the content of components; N is the number of components.
If at each vertex of the simplex we take the content of one of the components of the mixture as 1, then in the abovementioned normalization condition, all the points located inside the twodimensional regular simplex whose number of vertices equals the number of components of the mixture will satisfy. For example, in our case, this simplex is an equilateral triangle.
To each point of such a simplex, there corresponds a mixture of the corresponding composition, and any combination of the relative content of the components corresponds to a specific point on the simplex.
When planning the experiment in the form of “compositionproperty” diagrams, it is assumed that the property under investigation is a continuous function of the argument and is described with sufficient accuracy by the polynomial. The response surfaces in multicomponent systems have a complicated form and, for an adequate description of them, the necessary polynomials of a high degree.
For threecomponent mixtures, we write down a possible polynomial ()
Calculation of the coefficients in the regression equation and checking its adequacy were carried out using the program STATISTICA 12.
The response surface in the compositionproperty diagrams was represented using isolines. The response functions were coercive field (H_{c}), saturation magnetization (M_{s}), resonant field (H_{R}), width of the EPR peak (ΔH_{pp}), and intensity of the EPR peak of the spectrum (I, a.u.).
3. Results and Discussion
The magnetic properties of ferrites obtained under the action of CNP on the suspension of iron(II) and Me(II) polyhydroxides complexes are dependent on the pH of the solution of the iron(II) salt or the Fe(OH)_{2} suspension, the temperature of the reaction medium, the rate of oxidation, its activity and efficiency distribution in the reaction medium, and the concentration of iron(II) ions in the solution or iron(II) hydroxide in suspension [12–15]. But one of the most important factors is the cationic composition of ferrites [16–22]. In accordance with the simplex method, ten samples were synthesized and their properties were investigated.
Better samples are shown in Figures 1, 2, and 3. All results are shown in Table 2.
 
H_{c} is the coercive field; M_{s} is the saturation magnetization; H_{R} is the resonance field of the EPR spectrum, mT; ΔH_{p} is the line width between the points of maximum slope on the EPR spectrum, mT; I is the intensity of the EPR line of the spectrum, a.u; a is the lattice parameter, A. 
Mathematical processing of the experimental data using the program STATISTICA 12 allowed obtaining regression equations adequately describing the relationship between the magnetic indices and the composition of prototypes.
The resulting regression equations were used to construct isolines of the magnetic characteristics of ferrites in the factorial space under study (Figures 3 and 4).
(a)
(b)
(c)
(d)
The highest value of the coercive field corresponds to the composition containing the maximum number of cobalt cations. An increase in the content of cobalt cations leads to an increase in the coercive field in all compositions. A positive effect of nickel cations on the saturation magnetization of ferrites along the side of the triangle NiZn and opposite on the NiCo side was also observed (Figure 4).
Moreover, the value of the saturation magnetization depends more on the content of cobalt cations. The highest magnetic indices correspond to the maximum content of cobalt. Thus, magnetic ferrites with an increased coercive field correspond to compositions 1,2,3, and magnetic ferrites with low coercive field 4,5,6,7. In the diagrams, an equilateral triangle with coordinates of the vertices of Co (1,0,0) Ni (0.75,0,0) Zn (0.25,0,0) can be identified, which corresponds to a region of higher values of the saturation magnetization.
Comparison of the main characteristics on the EPR spectra with magnetic properties makes it possible to explain the mechanism of action and to establish the contribution of the presence of ferrimagnetic cations and the degree of inversion of spinel. Xray phase analysis showed that the samples contain the ferromagnetic phase probably MeFe_{2}O_{4} and antiferromagnetic αFe_{2}O_{3}.
The magnetic characteristics correspond to the data of Xray phase analysis and EPR data (Figures 4 and 5).
(a)
(b)
(c)
(d)
All EPR spectra have a symmetric broad resonance signal, but their line width (ΔH_{pp}) and resonant magnetic field (H_{R}) are very different (Table 2). It can be seen from Figures 5(a) and 5(b) that there is an increase in the resonance field and a change in the line width with an increase in the molar concentration of cobalt and nickel cations. It is seen that ΔH_{pp} is narrow; the intensity of the peaks is larger for a higher concentration of Zn. The spectrum of the cobalt ferrite sample shows a rather wide signal (ΔH_{pp} = 398.7 mT). It is interesting that the effect of cobalt cations on the main characteristics of the EPR spectrum is much more significant than that of nickel. Consider the equation [21] where ΔH_{pp} is the width of the EPR line of the spectrum, K_{1} is the anisotropy, p is the porosity, Н_{е} is the noneddy currents, and Н_{id} is the inhomogeneous demagnetization.
Earlier studies have shown that the magnetic parameters of ferrites, in the system CoONiO, ZnO, depend on the composition. An increase in the cobalt content in the system leads to an increase in the coercive field and the saturation magnetization. The increase in the content of cobalt cations in ferrites from 0 to 1.0 mol. shares causes a significant increase in the coercive field from 23 to 1140 Oe. This fact is confirmed by a shift in the values of the lattice parameter d (8.35 A) to a region of lower values (8.32 A) as well as an increase in the bandwidth on the EPR spectrum.
From the values of coercivity (H_{c}) and saturation magnetization (M_{s}), the value of the anisotropy constant K_{1} can be calculated using the following relation:
Then
Taking into account that the largest value of the anisotropy constant corresponds to cobaltcontaining ferrites, the contribution of the first term to equation (6) is the greatest. This determines a fairly broad peak of the EPR spectrum for samples 13.
The compositionproperty diagrams for the value of the resonance field and the line width correlate with the diagram for magnetic saturation. The resonant magnetic field increases with increasing content in cobalt and nickel samples. Reducing the width of the line, i.e., the narrowing of the derivative of the resonance signal with increasing content of Zn^{2+} and Ni^{2+} is associated with various causes. For zinc cations, first of all, these are their diamagnetic properties. For Ni^{2+} ions, this can be caused by their redistribution along sublattices and a decrease in the magnetic moment of the sublattice B, taking into account the vacancies formed. This causes a general decrease in the magnetic moment. In accordance with this, a decrease in the resonant field for nickel ferrite occurs in accordance with formula
With an increase in the content of zinc cations, an increase in the intensity of the peaks and their narrowing are observed. Since the anisotropy constant for zinc ferrite is the smallest, it can be assumed that this is primarily due to the decrease of the first term in equation (6); the second term is also small, so the total value is also small. In these systems, the concentration of diamagnetic Zn^{2+} ions plays a decisive role. The existing dependence of H_{pp} on the concentration of Zn is due to the superexchange interaction between Ni^{2+} and Fe^{2+} through nonmagnetic O^{2−} ions.
Almost complete coincidence of the isolines for the graphs M_{s} = f (Ni, Co, Zn) and H_{r} = f (Ni, Co, Zn) makes it possible to assume that the main factor determining the ferrite magnet is the cation distribution over the sublattices with allowance for the concentration of diamagnetic ions.
4. Conclusions
The article is devoted to the analysis of changes in the magnetic characteristics of ferrites in the Fe_{2}O_{3}CoOZnO system by the simplex method. Ferrites of NiZn, CoZn, and CoNi were synthesized in the form of nanoparticles using a new method for processing contact nonequilibrium lowtemperature plasma. The crystalline, magnetic, and microstructure of the finished crystallites were elucidated using several methods. The macroscopic characteristics of magnetic materials are inherently rooted in their atomic structure. Understanding the crystal structure is necessary for the synthesis of magnetic nanomaterials with optimal properties. For spinel ferrites, in particular, the choice of a bivalent cation and its distribution between the tetrahedral and octahedral sites directly determine their magnetic behavior. The effect of the mutual influence of the content of different cations on the saturation magnetization and the coercive field was investigated using the simplexlattice method. A magnetic investigation using a vibrational magnetometer shows that under these synthesis conditions, low magnetization values for NiZn ferrites and high magnetization values for the whole CoZn and CoNi ferrite series are observed. The EPR spectra show that the value of the resonant field and line width corresponds to the value of the magnetic saturation. In this work, a new method of synthesis of combustion is the nanoferrite used to produce NiZn. The EPR spectra of ferrites are explained on the basis of superexchange interaction.
Data Availability
Previously described method simplexlattice design was used to support this study and is available at https://books.google.com.ua/. This prior study is cited at the relevant place within the text as reference [11].
Conflicts of Interest
The authors declare that they have no competing interests.
References
 A. B. Gadkari, T. J. Shinde, and P. N. Vasambekar, “Ferrite gas sensors,” IEEE Sensors Journal, vol. 11, no. 4, pp. 849–861, 2011. View at: Publisher Site  Google Scholar
 W. Hu, N. Qin, G. Wu, Y. Lin, S. Li, and D. Bao, “Opportunity of spinel ferrite materials in nonvolatile memory device applications based on their resistive switching performances,” Journal of the American Chemical Society, vol. 134, no. 36, pp. 14658–14661, 2012. View at: Publisher Site  Google Scholar
 L. Živanov, M. Damnjanović, N. Blaž, A. Marić, M. Kisić, and G. Radosavljević, “Soft ferrite applications,” in Magnetic, Ferroelectric, and Multiferroic Metal Oxides, pp. 387–409, Elsevier, 2018. View at: Publisher Site  Google Scholar
 V. M. Chernyshev and N. P. Shabelskaya, “Comparative analysis of catalytic activity in complex NiOCuOFe_{2}O_{3}Cr_{2}O_{3} Oxide system of different production technologies,” Materials Science Forum, vol. 870, pp. 118–122, 2016. View at: Publisher Site  Google Scholar
 R. S. Melo, P. Banerjee, and A. Franco, “Hydrothermal synthesis of nickel doped cobalt ferrite nanoparticles: optical and magnetic properties,” Journal of Materials Science: Materials in Electronics, vol. 29, no. 17, pp. 14657–14667, 2018. View at: Publisher Site  Google Scholar
 L. A. Frolova and A. A. Pivovarov, “Investigation of conditions for ultrasoundassisted preparation of nickel ferrite,” High Energy Chemistry, vol. 49, no. 1, pp. 10–15, 2015. View at: Publisher Site  Google Scholar
 L. A. Frolov, A. A. Pivovarov, A. S. Baskevich, and A. I. Kushnerev, “Structure and properties of nickel ferrites produced by glow discharge in the Fe^{2+}Ni^{2+}SO_{4}^{2−}OH^{−} system,” Russian Journal of Applied Chemistry, vol. 87, no. 8, pp. 1054–1059, 2014. View at: Publisher Site  Google Scholar
 R. N. Bhowmik and K. S. Aneeshkumar, “Low temperature ferromagnetic properties, magnetic field induced spin order and random spin freezing effect in Ni_{1.5}Fe_{1.5}O_{4} ferrite; prepared at different pH values and annealing temperatures,” Journal of Magnetism and Magnetic Materials, vol. 460, pp. 177–187, 2018. View at: Publisher Site  Google Scholar
 G. AvramovicCingara, J. Zweck, J. D. Giallonardo, G. Palumbo, and U. Erb, “Magnetic domain structure in nanocrystalline nickel electrodeposits,” Journal of Applied Physics, vol. 123, no. 23, pp. 234301–234301, 2018. View at: Publisher Site  Google Scholar
 R. N. Bhowmik, R. Ranganathan, R. Nagarajan, B. Ghosh, and S. Kumar, “Role of straininduced anisotropy on magnetic enhancement in mechanically alloyed Co_{0.2}Zn_{0.8}Fe_{2}O_{4} nanoparticle,” Physical Review B, vol. 72, no. 9, 2005. View at: Publisher Site  Google Scholar
 J. A. Cornell, Experiments with Mixtures: Designs, Models, and the Analysis of Mixture Data, vol. 403, John Wiley & Sons, 2011.
 C. Singh, S. Bansal, and S. Singhal, “Synthesis of Zn_{1−x}Co_{x}Fe_{2}O_{4}/MWCNTs nanocomposites using reverse micelle method: investigation of their structural, magnetic, electrical, optical and photocatalytic properties,” Physica B: Condensed Matter, vol. 444, pp. 70–76, 2014. View at: Publisher Site  Google Scholar
 M. Sundararajan, L. John Kennedy, and J. Judith Vijaya, “Synthesis and characterization of cobalt substituted zinc ferrite nanoparticles by microwave combustion method,” Journal of Nanoscience and Nanotechnology, vol. 15, no. 9, pp. 6719–6728, 2015. View at: Publisher Site  Google Scholar
 A. Manikandan, L. J. Kennedy, M. Bououdina, and J. J. Vijaya, “Synthesis, optical and magnetic properties of pure and Codoped ZnFe_{2}O_{4} nanoparticles by microwave combustion method,” Journal of Magnetism and Magnetic Materials, vol. 349, pp. 249–258, 2014. View at: Publisher Site  Google Scholar
 I. Zālīte, G. Heidemane, A. Krūmiņa, D. Rašmane, and M. Maiorov, “ZnFe_{2}O_{4} containing nanoparticles: synthesis and magnetic properties,” Materials Science and Applied Chemistry, vol. 34, no. 1, pp. 38–44, 2017. View at: Publisher Site  Google Scholar
 K. Sun, Z. Pu, Y. Yang et al., “Rietveld refinement, microstructure and ferromagnetic resonance linewidth of irondeficiency NiCuZn ferrites,” Journal of Alloys and Compounds, vol. 681, pp. 139–145, 2016. View at: Publisher Site  Google Scholar
 M. Su, C. Liao, T. Chan et al., “Incorporation of cadmium and nickel into ferrite spinel solid solution: Xray diffraction and Xray absorption fine structure analyses,” Environmental Science & Technology, vol. 52, no. 2, pp. 775–782, 2018. View at: Publisher Site  Google Scholar
 T. R. Tatarchuk, N. D. Paliychuk, M. Bououdina et al., “Effect of cobalt substitution on structural, elastic, magnetic and optical properties of zinc ferrite nanoparticles,” Journal of Alloys and Compounds, vol. 731, pp. 1256–1266, 2018. View at: Publisher Site  Google Scholar
 B. Thangjam and I. Soibam, “Structural, electrical and magnetic properties of Mg doped NiCuZn nanoferrites synthesized by citrate precursor method,” International Journal of Applied Engineering Research, vol. 12, no. 23, pp. 13201–13206, 2017. View at: Google Scholar
 M. T. Jamil, J. Ahmad, S. H. Bukhari et al., “Effect on structural and optical properties of Znsubstituted cobalt ferrite CoFe_{2}O_{4},” Journal of Ovonic Research, vol. 3, no. 1, pp. 45–53, 2017. View at: Google Scholar
 C. M. Srivastava and M. J. Patni, “Ferromagnetic relaxation processes in polycrystalline magnetic insulators,” Journal of Magnetic Resonance, (1969), vol. 15, no. 2, pp. 359–366, 1974. View at: Publisher Site  Google Scholar
 R. N. Bhowmik, S. Kazhugasalamoorthy, R. Ranganathan, and A. K. Sinha, “Tuning of composite cubic spinel structure in Co_{1.75}Fe_{1.25}O_{4} spinel oxide by thermal treatment and its effects on modifying the ferromagnetic properties,” Journal of Alloys and Compounds, vol. 680, pp. 315–327, 2016. View at: Publisher Site  Google Scholar
Copyright
Copyright © 2018 Liliya Frolova and Oleg Khmelenko. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.