Insights into the effects of Mn substitution in CoFe₂O₄ nanoferrites involving high-frequency storage device applications

Abstract

Nanoferrites of the CoMn_xFe(_2−x)O₄ series (x = 0.00, 0.05, 0.10, 0.15, 0.20) were synthesized in this study using the sol–gel auto-combustion approach. The lattice constants were computed within the range of 8.312–8.406 Å, while crystallite sizes were estimated to range between 55.20 and 31.40 nm using the Scherrer method. The different functional groups were found to correlate with various absorption bands using Fourier transform infrared (FTIR) spectroscopy. Five active modes were identified by Raman spectroscopy, revealing vibration modes of O²⁻ ions at tetrahedral and octahedral locations. The ferromagnetic hysteresis loop was observed in all the synthesized samples, which can be explained by Neel’s model. The results showed that AC conductivity decreased with increasing Mn²⁺ content at the Fe²⁺ site, while the dielectric constant and dielectric loss increased with increasing frequency. Furthermore, the saturation magnetization (M_s), remnant magnetization (M_r), and coercivity (H_c) all showed declining trends with the increase in Mn²⁺ doping. Finally, the CoMn_0.20Fe_1.8O₄ samples showed M_s and M_r values ranging from 73.12 to 66.84 emu/g and from 37.77 to 51.89 emu/g, respectively, while H_c values ranged from 1939 to 1312 Oe, after which coercivity increased. Thus, the CoMn_0.20Fe_1.8O₄ sample can be considered a promising candidate for magnetic applications.

Keywords

nano ferrite / structural / sol–gel auto-combustion / impedance study / magnetic study

References

[1] KotnalaR, ShahJ. Ferrite materials: Nano to spintronics regime. Handbook of Magnetic Materials, 2015, 23: 291

[2] X.Y. Xiang, Z.H. Yang, G. Fang, et al., Tailoring tactics for optimizing microwave absorbing behaviors in ferrite materials, Mater. Today Phys., 36(2023), art. No. 101184.

[3] G. Chen, Z.J. Li, L.M. Zhang, et al., Mechanisms, design, and fabrication strategies for emerging electromagnetic wave-absorbing materials, Cell Rep. Phys. Sci., 5(2024), No. 7, art. No. 102097.

[4] G.J. Ma, D. Lan, Y. Zhang, et al., Microporous cobalt ferrite with bio-carbon loosely decorated to construct multi-functional composite for dye adsorption, anti-bacteria and electromagnetic protection, Small, 20(2024), No. 45, art. No. 2404449.

[5] S.J. Salih and W.M. Mahmood, Review on magnetic spinel ferrite (MFe₂O₄) nanoparticles: From synthesis to application, Heliyon, 9(2023), No. 6, art. No. e16601.

[6] BorhanAI, GhercăD, IordanAR, PalamaruMNSinghJP, ChaeKH, SrivastavaRC, CaltunOF. Classification and types of ferrites. Ferrite Nanostructured Magnetic Materials, 2023, Amsterdan, Elsevier

[7] AdarshgowdaN, Bhojya NaikHS, VishnuG, HareeshanaikS. Green synthesized manganese-doped cobalt ferrite photocatalysts for light driven degradation of dye and optoelectronic studies. Ceram. Int., 2024, 50(12): 22060

[8] ZhangSJ, LanD, ZhengJJ, et al.. Rational construction of heterointerfaces in biomass sugarcane-derived carbon for superior electromagnetic wave absorption. Int. J. Miner. Metall. Mater., 2024, 31(12): 2749

[9] LiXD, ZhuX, FengAL, AnMM, LiuPT, ZuYQ. Electrochemical and surface analysis investigation of corrosion inhibition performance: 6-Thioguanine, benzotriazole, and phosphate salt on simulated patinas of bronze relics. J. Mater. Res. Technol., 2024, 29: 5667

[10] DashB, RoutrayKL, SahaS, YoshimuraS, RathaS, RoutMK. Investigation of substitution of nickel cations in cobalt ferrite (CoFe₂O₄) nanoparticles and their influence on frequency and temperature dependent dielectric and magnetodielectric properties. Trans. Electr. Electron. Mater., 2024, 25(2): 232

[11] K.L. Routray, D. Sanyal, and D. Behera, Dielectric, magnetic, ferroelectric, and Mossbauer properties of bismuth substituted nanosized cobalt ferrites through glycine nitrate synthesis method, J. Appl. Phys., 122(2017), No. 22, art. No. 224104.

[12] SatishM, ShashankaHM, SahaS, et al.. Effect of high-anisotropic Co²⁺ substitution for Ni²⁺ on the structural, magnetic, and magnetostrictive properties of NiFe₂O₄: Implications for sensor applications. ACS Appl. Mater. Interfaces, 2023, 15(12): 15691

[13] ChakrabartyS, DuttaA, PalM. Effect of Mn and Ni codoping on ion dynamics of nanocrystalline cobalt ferrite: A structure property correlation study. Electrochim. Acta, 2015, 184: 70

[14] V.P. Thakare, O.S. Game, and S.B. Ogale, Ferromagnetism in metal oxide systems: Interfaces, dopants, and defects, J. Mater. Chem. C, 1(2013), No. 8, art. No. 1545.

[15] A.A. Ibiyemi, G.T. Yusuf, O. Akirinola, M. Orojo, B. Osuporu, and J. Lawal, Investigating the magnetic domain structure and photonics characters of singled phased hard ferromagnetic ferrite MFe₃O₄ (M = Co²⁺, Zn²⁺, Cd²⁺) compounds, J. Nig. Soc. Phys. Sci., 6(2024), No. 1, art. No. 1909.

[16] R. Jabbar, S.H. Sabeeh, and A.M. Hameed, Structural, dielectric and magnetic properties of Mn⁺² doped cobalt ferrite nanoparticles, J. Magn. Magn. Mater., 494(2020), art. No. 165726.

[17] M.S. Al Maashani, K.A. Khalaf, A.M. Gismelseed, and I.A. Al-Omari, The structural and magnetic properties of the nano-CoFe₂O₄ ferrite prepared by sol-gel auto-combustion technique, J. Alloy. Compd., 817(2020), art. No. 152786.

[18] S. Saha, K.L. Routray, P. Hota, et al., Structural, magnetic and dielectric properties of green synthesized Ag doped NiFe₂O₄ spinel ferrite, J. Mol. Struct., 1302(2024), art. No. 137409.

[19] K.L. Routray and S. Saha, Impact of CNTs incorporation on structural, optical and dielectric properties of Ag doped spinel CoFe₂O₄ nanohybrid and their photovoltaic possibilities, J. Inorg. Organomet. Polym. Mater., (2024). https://doi.org/10.1007/s10904-024-03137-w

[20] K.L. Routray and S. Saha, Graphene nanoplatelets anchored into Ag doped spinel CoFe₂O₄ nanohybrid: Synthesis, structural, electrical, superior dielectric and room temperature induced ferromagnetism performance for high frequency device application, Diamond Relat. Mater., 141(2024), art. No. 110680.

[21] RoutrayKL, SahaS, BeheraD. Insight into the anomalous electrical behavior, dielectric and magnetic study of Agdoped CoFe₂O₄ synthesised by okra extract-assisted green synthesis. J. Electron. Mater., 2020, 49(12): 7244

[22] S.A. Hassanzadeh-Tabrizi, Precise calculation of crystallite size of nanomaterials: A review, J. Alloy. Compd., 968(2023), art. No. 171914.

[23] X.H. Pang, S.Z. Ji, P. Zhang, et al., Interlayer doping of pseudocapacitive hydrated vanadium oxide via Mn²⁺ for high-performance aqueous zinc-ion battery, Electrochim. Acta, 441(2023), art. No. 141810.

[24] I.D. Vlaicu, M. Stefan, C. Radu, D.C. Culita, D. Radu, and D. Ghica, Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn²⁺ paramagnetic probes, Front. Chem., 11(2023), art. No. 1154219.

[25] P. Kumar, M.C. Mathpal, G.K. Inwati, et al., Study of defect-induced chemical modifications in spinel zinc–ferrites nanostructures by in-depth XPS investigation, Magnetochemistry, 9(2023), No. 1, art. No. 20.

[26] S.M. Ansari, D. Phase, Y.D. Kolekar, and C.V. Ramana, Effect of manganese-doping on the chemical and optical properties of cobalt ferrite nanoparticles, Mater. Sci. Eng. B, 300(2024), art. No. 117134.

[27] A.L. Kwiatkowski, P.V. Shvets, I.S. Timchenko, et al., Cobalt ferrite nanorods synthesized with a facile “green” method in a magnetic field, Nanomaterials, 14(2024), No. 6, art. No. 541.

[28] A. Joshi, R.C. Srivastava, R. Dhyani, and C.S. Joshi, Structural, magnetic, and dielectric properties of yttrium doped cobalt ferrite and their nanocomposites with polythiophene, J. Magn. Magn. Mater., 578(2023), art. No. 170812.

[29] S. Tiwari, G. Lal, H. Bhoi, K. Punia, S. Singh Meena, and S. Kumar, Coexistence of superparamagnetism and superspin glass in non-stoichiometric Zn_0.5Ca_0.5Fe₂O₄ nanoferrite, J. Magn. Magn. Mater., 570(2023), art. No. 170466.

[30] S.O. Aisida, T.C. Chibueze, M.H. Alnasir, et al., Microstructural and magneto-optical properties of Co_1−xNi_xFe₂O₄ nanocomposites for hyperthermia applications, Solid State Sci., 136(2023), art. No. 107107.

[31] S.M. Yadav, S. Kumar, M. Kumar, A. Ghosh, and D.S. Saini, High-temperature variable range hopping conduction and dielectric relaxation in CoFe₂O₄ ceramic, Open Ceram., 17(2024), art. No. 100517.

[32] X. Fan, T.G. Myers, B.D. Sukra, and G. Gabrielse, Measurement of the electron magnetic moment, Phys. Rev. Lett., 130(2023), No. 7, art. No. 071801.

[33] ShiB, LiangHS, XieZJ, ChangQ, WuHJ. Dielectric loss enhancement induced by the microstructure of CoFe₂O₄ foam to realize broadband electromagnetic wave absorption. Int. J. Miner. Metall. Mater., 2023, 30(7): 1388

[34] J.B. Collings, R. Rama-Eiroa, R.M. Otxoa, R.F.L. Evans, and R.W. Chantrell, Generalized form of the magnetic anisotropy field in micromagnetic and atomistic spin models, Phys. Rev. B, 107(2023), No. 6, art. No. 064413.

[35] A. Mahmood and A. Maqsood, Temperature and frequency-dependent electrical transport studies of manganese-doped zinc ferrite nanoparticles, Mater. Sci. Eng. B, 296(2023), art. No. 116615.

[36] H. Wang and L. Yang, Dielectric constant, dielectric loss, conductivity, capacitance and model analysis of electronic electroactive polymers, Polym. Test., 120(2023), art. No. 107965.

[37] R.J. Sengwa, N. Kumar, and M. Saraswat, Morphological, structural, optical, broadband frequency range dielectric and electrical properties of PVDF/PMMA/BaTiO₃ nanocomposites for futuristic microelectronic and optoelectronic technologies, Mater. Today Commun., 35(2023), art. No. 105625.

[38] PadhiPS, AjimshaRS, RaiSK, et al.. Process temperature-dependent interface quality and Maxwell–Wagner interfacial polarization in atomic layer deposited Al₂O₃/TiO₂ nanolaminates for energy storage applications. Nanoscale, 2023, 15(18): 8337

[39] M. Zulqarnain, S.S. Ali, M.A. Yaqub, et al., Spinel ferrites having conductive grains, resistive interfacial boundaries and relaxation mechanism for possible supercapacitor applications, Results Phys., 61(2024), art. No. 107732.

[40] A. Jain, C. Singh, S.K. Godara, R.B. Jotania, V. Kaur, and A.K. Sood, Investigating grain and grain boundary effects on charge transport and dielectrics in BaCo_xAl_xFe_12−2xO₁₉ nanoferrites, Phys. B: Condens. Matter, 690(2024), art. No. 416211.

[41] F. Eghdami and A. Gholizadeh, A correlation between microstructural and impedance properties of MnFe_2−xCo_xO₄ nanoparticles, Phys. B: Condens. Matter, 650(2023), art. No. 414551.

[42] M.J. Feng, Y. Feng, C.H. Zhang, et al., Enhanced high-temperature energy storage performance of all-organic composite dielectric via constructing fiber-reinforced structure, Energy Environ. Mater., 7(2024), No. 2, art. No. e12571.

[43] P. Halder and S. Bhattacharya, Debye to non-Debye type relaxation in MoO₃ doped glassy semiconductors: A portrait on microstructure and electrical transport properties, Phys. B: Condens. Matter, 648(2023), art. No. 414374.

[44] L. Zhang, Y.P. Pu, and M. Chen, Complex impedance spectroscopy for capacitive energy-storage ceramics: A review and prospects, Mater. Today Chem., 28(2023), art. No. 101353.

RIGHTS & PERMISSIONS

University of Science and Technology Beijing