Journal Home > Volume 11 , Issue 5

Ferrites are the most widely used microwave absorbing materials to deal with the threat of electromagnetic (EM) pollution. However, the lack of sufficient dielectric loss capacity is the main challenge that limits their applications. To cope with this challenge, three high-entropy (HE) spinel-type ferrite ceramics including (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4, (Mg0.2Fe0.2Co0.2Ni0.2Cu0.2)Fe2O4, and (Mg0.2Fe0.2Co0.2Ni0.2Zn0.2)Fe2O4 were designed and successfully prepared through solid state synthesis. The results show that all three HE MFe2O4 samples exhibit synergetic dielectric loss and magnetic loss. The good magnetic loss ability is due to the presence of magnetic components; while the enhanced dielectric properties are attributed to nano-domain, hopping mechanism of resonance effect and HE effect. Among three HE spinels, (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4 shows the best EM wave absorption performance, e.g., its minimum reflection loss (RLmin) reaches −35.10 dB at 6.78 GHz with a thickness of 3.5 mm, and the optimized effective absorption bandwidth (EAB) is 7.48 GHz from 8.48 to 15.96 GHz at the thickness of 2.4 mm. Due to the easy preparation and strong EM dissipation ability, HE MFe2O4 are promising as a new type of EM absorption materials.


menu
Abstract
Full text
Outline
About this article

High-entropy spinel ferrites MFe2O4 (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) with tunable electromagnetic properties and strong microwave absorption

Show Author's information Jiabin MAa,bBiao ZHAOa( )Huimin XIANGbFu-Zhi DAIbYi LIUcRui ZHANGdYanchun ZHOUb( )
Henan Key Laboratory of Aeronautical Materials and Application Technology, School of Materials Science and Engineering, Zhengzhou University of Aeronautics, Zhengzhou 450046, China
Science and Technology on Advanced Functional Composite Laboratory, Aerospace Research Institute of Materials & Processing Technology, Beijing 100076, China
School of Material Science and Engineering, Shaanxi University of Science and Technology, Xi’an 710021, China
School of Materials Science and Engineering, Luoyang Institute of Science and Technology, Luoyang 471023, China

Abstract

Ferrites are the most widely used microwave absorbing materials to deal with the threat of electromagnetic (EM) pollution. However, the lack of sufficient dielectric loss capacity is the main challenge that limits their applications. To cope with this challenge, three high-entropy (HE) spinel-type ferrite ceramics including (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4, (Mg0.2Fe0.2Co0.2Ni0.2Cu0.2)Fe2O4, and (Mg0.2Fe0.2Co0.2Ni0.2Zn0.2)Fe2O4 were designed and successfully prepared through solid state synthesis. The results show that all three HE MFe2O4 samples exhibit synergetic dielectric loss and magnetic loss. The good magnetic loss ability is due to the presence of magnetic components; while the enhanced dielectric properties are attributed to nano-domain, hopping mechanism of resonance effect and HE effect. Among three HE spinels, (Mg0.2Mn0.2Fe0.2Co0.2Ni0.2)Fe2O4 shows the best EM wave absorption performance, e.g., its minimum reflection loss (RLmin) reaches −35.10 dB at 6.78 GHz with a thickness of 3.5 mm, and the optimized effective absorption bandwidth (EAB) is 7.48 GHz from 8.48 to 15.96 GHz at the thickness of 2.4 mm. Due to the easy preparation and strong EM dissipation ability, HE MFe2O4 are promising as a new type of EM absorption materials.

Keywords: high-entropy ceramics (HECs), dielectric loss, magnetic loss, electromagnetic (EM) wave absorption, spinel-type ferrite

References(92)

[1]
Robinette CD, Silverman C, Jablon S. Effects upon health of occupational exposure to microwave radiation (radar). Am J Epidemiol 1980, 112: 39–53.
[2]
Balmori A. Electromagnetic pollution from phone masts. Effects on wildlife. Pathophysiology 2009, 16: 191–199.
[3]
Zhao B, Guo XQ, Zhao WY, et al. Yolk–shell Ni@SnO2 composites with a designable interspace to improve the electromagnetic wave absorption properties. ACS Appl Mater Interfaces 2016, 8: 28917–28925.
[4]
Wang L, Yu XF, Li X, et al. MOF-derived yolk–shell Ni@C@ZnO Schottky contact structure for enhanced microwave absorption. Chem Eng J 2020, 383: 123099.
[5]
Zhou YC, Zhao B, Chen H, et al. Electromagnetic wave absorbing properties of TMCs (TM = Ti, Zr, Hf, Nb and Ta) and high entropy (Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C. J Mater Sci Technol 2021, 74: 105–118.
[6]
Narang SB, Pubby K. Nickel spinel ferrites: A review. J Magn Magn Mater 2021, 519: 167163.
[7]
Zhao B, Deng JS, Zhang R, et al. Recent advances on the electromagnetic wave absorption properties of Ni based materials. Eng Sci 2018, 3: 5–40.
[8]
Quan B, Liang XH, Ji GB, et al. Dielectric polarization in electromagnetic wave absorption: Review and perspective. J Alloys Compd 2017, 728: 1065–1075.
[9]
Singh P, Babbar VK, Razdan A, et al. Complex permeability and permittivity, and microwave absorption studies of Ca(CoTi)xFe12−2xO19 hexaferrite composites in X-band microwave frequencies. Mater Sci Eng B 1999, 67: 132– 138.
[10]
Zhao B, Guo XQ, Zhao WY, et al. Facile synthesis of yolk– shell Ni@void@SnO2(Ni3Sn2) ternary composites via galvanic replacement/Kirkendall effect and their enhanced microwave absorption properties. Nano Res 2017, 10: 331–343.
[11]
Manna K, Srivastava SK. Fe3O4@carbon@polyaniline trilaminar core–shell composites as superior microwave absorber in shielding of electromagnetic pollution. ACS Sustain Chem Eng 2017, 5: 10710–10721.
[12]
Joseph N, Varghese J, Sebastian MT. Graphite reinforced polyvinylidene fluoride composites an efficient and sustainable solution for electromagnetic pollution. Compos B Eng 2017, 123: 271–278.
[13]
Sun BB, Sun SJ, He P, et al. Asymmetric layered structural design with segregated conductive network for absorption-dominated high-performance electromagnetic interference shielding. Chem Eng J 2021, 416: 129083.
[14]
Zhao B, Wang S, Zhao CX, et al. Synergism between carbon materials and Ni chains in flexible poly(vinylidene fluoride) composite films with high heat dissipation to improve electromagnetic shielding properties. Carbon 2018, 127: 469–478.
[15]
Qiao J, Xu DM, Lv LF, et al. Self-assembled ZnO/Co hybrid nanotubes prepared by electrospinning for lightweight and high-performance electromagnetic wave absorption. ACS Appl Nano Mater 2018, 1: 5297–5306.
[16]
Huang XG, Zhang J, Rao WF, et al. Tunable electromagnetic properties and enhanced microwave absorption ability of flaky graphite/cobalt zinc ferrite composites. J Alloys Compd 2016, 662: 409–414.
[17]
Huang XG, Zhang J, Wang W, et al. Effect of pH value on electromagnetic loss properties of Co–Zn ferrite prepared via coprecipitation method. J Magn Magn Mater 2016, 405: 36–41.
[18]
Nakamura T, Miyamoto T, Yamada Y. Complex permeability spectra of polycrystalline Li–Zn ferrite and application to EM-wave absorber. J Magn Magn Mater 2003, 256: 340– 347.
[19]
Jia JG, Liu CY, Ma N, et al. Exchange coupling controlled ferrite with dual magnetic resonance and broad frequency bandwidth in microwave absorption. Sci Technol Adv Mater 2013, 14: 045002.
[20]
Feng AL, Hou TQ, Jia ZR, et al. Synthesis of a hierarchical carbon fiber@cobalt ferrite@manganese dioxide composite and its application as a microwave absorber. RSC Adv 2020, 10: 10510–10518.
[21]
Houbi A, Aldashevich ZA, Atassi Y, et al. Microwave absorbing properties of ferrites and their composites: A review. J Magn Magn Mater 2021, 529: 167839.
[22]
Lei CL, Du YW. Tunable dielectric loss to enhance microwave absorption properties of flakey FeSiAl/ferrite composites. J Alloys Compd 2020, 822: 153674.
[23]
Xiang HM, Xing Y, Dai FZ, et al. High-entropy ceramics: Present status, challenges, and a look forward. J Adv Ceram 2021, 10: 385–441.
[24]
Rost CM, Sachet E, Borman T, et al. Entropy-stabilized oxides. Nat Commun 2015, 6: 8485.
[25]
Oses C, Toher C, Curtarolo S. High-entropy ceramics. Nat Rev Mater 2020, 5: 295–309.
[26]
Chen H, Xiang HM, Dai FZ, et al. High entropy (Yb0.25Y0.25Lu0.25Er0.25)2SiO5 with strong anisotropy in thermal expansion. J Mater Sci Technol 2020, 36: 134– 139.
[27]
Zhao ZF, Chen H, Xiang HM, et al. High entropy defective fluorite structured rare-earth niobates and tantalates for thermal barrier applications. J Adv Ceram 2020, 9: 303– 311.
[28]
Sun YN, Xiang HM, Dai FZ, et al. Preparation and properties of CMAS resistant bixbyite structured high-entropy oxides RE2O3 (RE = Sm, Eu, Er, Lu, Y, and Yb): Promising environmental barrier coating materials for Al2O3f/Al2O3 composites. J Adv Ceram 2021, 10: 596–613.
[29]
Zhao ZF, Xiang HM, Dai FZ, et al. (TiZrHf)P2O7: An equimolar multicomponent or high entropy ceramic with good thermal stability and low thermal conductivity. J Mater Sci Technol 2019, 35: 2227–2231.
[30]
Sarkar A, Loho C, Velasco L, et al. Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency. Dalton Trans 2017, 46: 12167–12176.
[31]
Bérardan D, Franger S, Dragoe D, et al. Colossal dielectric constant in high entropy oxides. Phys Status Solidi RRL Rapid Res Lett 2016, 10: 328–333.
[32]
Musicó B, Wright Q, Ward TZ, et al. Tunable magnetic ordering through cation selection in entropic spinel oxides. Phys Rev Mater 2019, 3: 104416.
[33]
Chen H, Zhao B, Zhao ZF, et al. Achieving strong microwave absorption capability and wide absorption bandwidth through a combination of high entropy rare earth silicide carbides/rare earth oxides. J Mater Sci Technol 2020, 47: 216–222.
[34]
Zhang WM, Dai FZ, Xiang HM, et al. Enabling highly efficient and broadband electromagnetic wave absorption by tuning impedance match in high-entropy transition metal diborides (HE TMB2). J Adv Ceram 2021, 10: 1299– 1316.
[35]
Zhang WM, Zhao B, Xiang HM, et al. One-step synthesis and electromagnetic absorption properties of high entropy rare earth hexaborides (HE REB6) and high entropy rare earth hexaborides/borates (HE REB6/HE REBO3) composite powders. J Adv Ceram 2021, 10: 62–77.
[36]
Zhang WM, Zhao B, Ni N, et al. High entropy rare earth hexaborides/tetraborides (HE REB6/HE REB4) composite powders with enhanced electromagnetic wave absorption performance. J Mater Sci Technol 2021, 87: 155–166.
[37]
Radoń A, Hawełek Ł, Łukowiec D, et al. Dielectric and electromagnetic interference shielding properties of high entropy (Zn,Fe,Ni,Mg,Cd)Fe2O4 ferrite. Sci Rep 2019, 9: 20078.
[38]
Mohammadabadi FH, Masoudpanah SM, Alamolhoda S, et al. Electromagnetic microwave absorption properties of high entropy spinel ferrite ((MnNiCuZn)1−xCoxFe2O4)/ graphene nanocomposites. J Mater Res Technol 2021, 14: 1099–1111.
[39]
Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr Sect A 1976, 32: 751–767.
[40]
Miles PA, Westphal WB, von Hippel A. Dielectric spectroscopy of ferromagnetic semiconductors. Rev Mod Phys 1957, 29: 279–307.
[41]
Takahashi S, Kan A, Ogawa H. Microwave dielectric properties and crystal structures of spinel-structured MgAl2O4 ceramics synthesized by a molten-salt method. J Eur Ceram Soc 2017, 37: 1001–1006.
[42]
Wilson D, Langell MA. XPS analysis of oleylamine/oleic acid capped Fe3O4 nanoparticles as a function of temperature. Appl Surf Sci 2014, 303: 6–13.
[43]
Vanidha D, Arunkumar A, Achary SN, et al. Unusual occupancy of more Fe3+ ions at A-site and enhanced metallic magnetization in nano Mg0.5Zn0.5Fe2O4. J Mol Struct 2014, 1076: 105–114.
[44]
Wang J, Scholl A, Zheng H, et al. Response to comment on “epitaxial BiFeO3 multiferroic thin film heterostructures”. Science 2005, 307: 1203.
[45]
Oumezzine E, Hcini S, Rhouma FIH, et al. Frequency and temperature dependence of conductance, impedance and electrical modulus studies of Ni0.6Cu0.4Fe2O4 spinel ferrite. J Alloys Compd 2017, 726: 187–194.
[46]
Shi EW, Yuan RL, Chen ZZ, et al. An introduction to computational crystallography: The relationship between aluminum-based spinel structures and their morphologies. Sci China Ser E 2003, 46: 259–270.
[47]
Zhou YC, Switzer JA. Electrochemical deposition and microstructure of copper (I) oxide films. Scripta Mater 1998, 38: 1731–1738.
[48]
Zhang L, Wang YZ, Liu BB, et al. Characterization and property of magnetic ferrite ceramics with interesting multilayer structure prepared by solid-state reaction. Ceram Int 2021, 47: 10927–10939.
[49]
Naik PP, Hasolkar SS, Kothawale MM, et al. Altering saturation magnetization of manganese zinc ferrite nanoparticles by doping with rare earth Nd+3 ions. Phys B Condens Matter 2020, 584: 412111.
[50]
Wang Y, Li LP, Zhang YL, et al. Growth kinetics, cation occupancy, and magnetic properties of multimetal oxide nanoparticles: A case study on spinel NiFe2O4. J Phys Chem C 2017, 121: 19467–19477.
[51]
Wu JT, Li N, Xu J, et al. Partially inverse spinel ZnFe2O4 with high saturation magnetization synthesized via a molten salt route. Appl Phys Lett 2011, 99: 202505.
[52]
Zhao DL, Zeng XW, Xia QS, et al. Preparation and coercivity and saturation magnetization dependence of inductive heating property of Fe3O4 nanoparticles in an alternating current magnetic field for localized hyperthermia. J Alloys Compd 2009, 469: 215–218.
[53]
Nonkumwong J, Ananta S, Jantaratana P, et al. Phase formation, morphology and magnetic properties of MgFe2O4 nanoparticles synthesized by hydrothermal technique. J Magn Magn Mater 2015, 381: 226–234.
[54]
Owen J. The colours and magnetic properties of hydrated iron group salts, and evidence for covalent bonding. Proc R Soc Lond A 1955, 227: 183–200.
[55]
Anderson PW. Antiferromagnetism. Theory of superexchange interaction. Phys Rev 1950, 79: 350–356.
[56]
Halpern V. A generalized mechanism for superexchange. Proc R Soc Lond A 1966, 291: 113–128.
[57]
Li HH, Feng ZK, He HH, et al. Effects of Fe2+ content in raw materials on Mn–Zn ferrite magnetic properties. J Magn Magn Mater 2001, 237: 153–157.
[58]
Anderson PW, Hasegawa H. Considerations on double exchange. Phys Rev 1955, 100: 675–681.
[59]
Tong W, Zhang B, Tan S, et al. Probability of double exchange between Mn and Fe in LaMn1−xFexO3. Phys Rev B 2004, 70: 014422.
[60]
Tilley RJD. Understanding Solids: The Science of Materials. 2nd edn. West Sussex (UK): John Wiley & Sons Ltd, 2013.
[61]
Stoppels D. Developments in soft magnetic power ferrites. J Magn Magn Mater 1996, 160: 323–328.
[62]
Thakur P, Chahar D, Taneja S, et al. A review on MnZn ferrites: Synthesis, characterization and applications. Ceram Int 2020, 46: 15740–15763.
[63]
Gao Y. The Fundamental of Advanced Measuring Instruments for Materials. Beijing: Tsinghua University Press, 2008. (in Chinese)
[64]
O’Neill D, Bowman RM, Gregg JM. Dielectric enhancement and Maxwell–Wagner effects in ferroelectric superlattice structures. Appl Phys Lett 2000, 77: 1520–1522.
[65]
Deng LJ, Zhou PH, Xie JL, et al. Characterization and microwave resonance in nanocrystalline FeCoNi flake composite. J Appl Phys 2007, 101: 103916.
[66]
Haque MM, Huq M, Hakim MA. Densification, magnetic and dielectric behaviour of Cu-substituted Mg–Zn ferrites. Mater Chem Phys 2008, 112: 580–586.
[67]
Hou ZR, Xiang J, Zhang XK, et al. Microwave absorption properties of single- and double-layer absorbers based on electrospun nickel–zinc spinel ferrite and carbon nanofibers. J Mater Sci Mater Electron 2018, 29: 12258–12268.
[68]
Iwauchi K. Dielectric properties of fine particles of Fe3O4 and some ferrites. Jpn J Appl Phys 1971, 10: 1520–1528.
[69]
Lakhtakia A. An electromagnetic trinity from “negative permittivity” and “negative permeability”. Int J Infrared Millim Waves 2002, 23: 813–818.
[70]
Wang ZY, Sun K, Xie PT, et al. Epsilon-negative BaTiO3/ Cu composites with high thermal conductivity and yet low electrical conductivity. J Materiomics 2020, 6: 145–151.
[71]
Dar MA, Verma V, Gairola SP, et al. Low dielectric loss of Mg doped Ni–Cu–Zn nano-ferrites for power applications. Appl Surf Sci 2012, 258: 5342–5347.
[72]
Akhtar MN, Rahman A, Sulong AB, et al. Structural, spectral, dielectric and magnetic properties of Ni0.5MgxZn0.5−xFe2O4 nanosized ferrites for microwave absorption and high frequency applications. Ceram Int 2017, 43: 4357–4365.
[73]
Xie PT, Zhang ZD, Wang ZY, et al. Targeted double negative properties in silver/silica random metamaterials by precise control of microstructures. Res Wash D C 2019, 2019: 1021368.
[74]
Glendening ED, Weinhold F. Natural resonance theory: I. General formalism. J Comput Chem 1998, 19: 593–609.
DOI
[75]
Ma Z, Liu QF, Yuan J, et al. Analyses on multiple resonance behaviors and microwave reflection loss in magnetic Co microflowers. Phys Status Solidi B 2012, 249: 575–580.
[76]
Luo H, Gong RZ, Wang X, et al. Fe3O4 cladding enhanced magnetic natural resonance and microwave absorption properties of Fe0.65Co0.35 alloy flakes. J Alloys Compd 2015, 646: 345–350.
[77]
Zhao B, Zhao WY, Shao G, et al. Morphology-control synthesis of a core–shell structured NiCu alloy with tunable electromagnetic-wave absorption capabilities. ACS Appl Mater Interfaces 2015, 7: 12951–12960.
[78]
Zhao B, Shao G, Fan BB, et al. Investigation of the electromagnetic absorption properties of Ni@TiO2 and Ni@SiO2 composite microspheres with core–shell structure. Phys Chem Chem Phys 2015, 17: 2531–2539.
[79]
Singh J, Singh C, Kaur D, et al. Development of doped Ba–Sr hexagonal ferrites for microwave absorber applications: Structural characterization, tunable thickness, absorption peaks and electromagnetic parameters. J Alloys Compd 2021, 855: 157242.
[80]
Wang GZ, Peng XG, Yu L, et al. Enhanced microwave absorption of ZnO coated with Ni nanoparticles produced by atomic layer deposition. J Mater Chem A 2015, 3: 2734–2740.
[81]
Han T, Luo RY, Cui GY, et al. Effect of fibre directionality on the microwave absorption properties of 3D braided SiCf/SiC composites. Ceram Int 2019, 45: 7797–7803.
[82]
Qian K, Yao ZJ, Lin HY, et al. The influence of Nd substitution in Ni–Zn ferrites for the improved microwave absorption properties. Ceram Int 2020, 46: 227–235.
[83]
Liu JL, Zhang P, Zhang XK, et al. Synthesis and microwave absorbing properties of La-doped Sr-hexaferrite nanopowders via sol–gel auto-combustion method. Rare Met 2017, 36: 704–710.
[84]
Wang TS, Liu ZH, Lu MM, et al. Graphene–Fe3O4 nanohybrids: Synthesis and excellent electromagnetic absorption properties. J Appl Phys 2013, 113: 024314.
[85]
Mandal D, Gorai A, Mandal K. Electromagnetic wave trapping in NiFe2O4 nano-hollow spheres: An efficient microwave absorber. J Magn Magn Mater 2019, 485: 43–48.
[86]
Huang XG, Zhang J, Lai M, et al. Preparation and microwave absorption mechanisms of the NiZn ferrite nanofibers. J Alloys Compd 2015, 627: 367–373.
[87]
Bhattacharya P, Hatui G, Mandal A, et al. Investigation of microwave absorption property of the core–shell structured Li0.4Mg0.6Fe2O4/TiO2 nanocomposite in X-band region. J Alloys Compd 2014, 590: 331–340.
[88]
Wang Y, Wu XM, Zhang WZ, et al. 3D heterostructure of graphene@Fe3O4@WO3@PANI: Preparation and excellent microwave absorption performance. Synth Met 2017, 231: 7–14.
[89]
Wang S, Ren HD, Lian W, et al. Purification and dissociation of raw palygorskite through wet ball milling as a carrier to enhance the microwave absorption performance of Fe3O4. Appl Clay Sci 2021, 200: 105915.
[90]
Song LL, Duan YP, Liu J, et al. Insight into electromagnetic absorbing performance of MnO2 from two dimensions: Crystal structure and morphology design. Mater Charact 2020, 163: 110300.
[91]
Su K, Wang Y, Hu KX, et al. Ultralight and high-strength SiCnw@SiC foam with highly efficient microwave absorption and heat insulation properties. ACS Appl Mater Interfaces 2021, 13: 22017–22030.
[92]
Bora PJ, Harstad SM, Gupta S, et al. Gadolinium silicide (Gd5Si4) nanoparticles for tuneable broad band microwave absorption. Mater Res Express 2019, 6: 055053.
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 23 September 2021
Revised: 29 December 2021
Accepted: 08 January 2022
Published: 20 April 2022
Issue date: May 2022

Copyright

© The Author(s) 2022.

Acknowledgements

This work is supported by the National Natural Science Foundation of China (Grant Nos. 51802289 and 51972089). Financial supports of the Science Foundation for the Excellent Youth Scholars of Henan Province (Grant No. 212300410089) and the Support Program for Scientific and Technological Innovation Talents of Higher Education in Henan Province (Grant No. 21HASTIT004) are acknowledged.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Return