Low Temperature Heat Capacity of Zn Substituted Cobalt Ferrite Nanosphere: The Relation between Magnetic Properties and Microstructure

Abstract

Co(_1−x)Zn _xFe₂O₄ nanospheres (x = 0, 0.5, 0.8) with a unidirectional cubic spinel structure were prepared by a solvothermal method. By using a range of theoretical and empirical models, the experimental heat capacity values were fitted as a function of temperature over a suitable temperature range to explain the possible relationship between the magnetic properties and microstructure of the nanospheres. As a result, at a low temperature (T < 10 K), the parameter B _fsw decreases with increasing Zn concentration, implying that the exchange interaction between A and B sites decreases. At a relatively high temperature (T > 50 K), the Debye temperature decreases with increasing Zn concentration, which is due to the weakening of the interatomic bonding force after the addition of non-magnetic materials to the CoFe₂O₄ spinel ferrite.

Keywords

Co-Zn spinal ferrite nanospheres / magnetic properties / heat capacity / thermodynamic functions / PPMS

References

[1] Muhammad A R, Athar J, Muhammad N R, et al. Understanding the Structural, Electronic, Magnetic and Optical Properties of Spinel MFe₂O₄ (M = Mn, Co, Ni) Ferrites[J]. Ceram. Int., 2020, 46(4): 4976-4983.

[2] Arévalo-Cid P, Isasi J, Alcolea M, et al. Comparative Structural, Morphological and Magnetic Study of MFe₂O₄ Nanopowders Prepared by Different Synthesis Routes[J]. Materials Research Bulletin, 2020, 123: 110 726.

[3] Patil V G, Shirsath S E, More S D, et al. Effect of Zinc Substitution on Structural and Elastic Properties of Cobalt Ferrite[J]. J. Alloys Compd, 2009, 488(1): 199-203.

[4] Fan C C, Zhai X W, Chen L, et al. Synthesis and Electrocatalytic Mechanism of Ultrafine MFe₂O₄ (M: Co, Ni, and Zn) Nanocrystallites: M/Fe Synergistic Effects on the Electrochemical Detection of Cu(II) and Hydrogen Evolution Reaction Performances[J]. J. Mater. Chem. A, 2021, 9(39): 22277-22290.

[5] Li R, Cen W, Yuan Y, et al. First Principle Calculation of Electromagnetic Mechanism for Fe₂Si Bulk Material[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed, 2019, 34(1): 64-68.

[6] Yogendra K, Alfa S, Parasharam M S. Impact of Different Morphologies of CoFe2O4 Nanoparticles for Tuning of Structural, Optical and Magnetic Properties[J]. Journal of Alloys and Compounds, 2019, 778: 398-409.

[7] Xie X B, Wang B L, Wang Y K, et al. Spinel Structured MFe₂O₄(M = Fe, Co, Ni, Mn, Zn) and Their Composites for Microwave Absorption: A Review[J]. Chemical Engineering Journal, 2022, 428: 131 160.

[8] Kasenov B K, Sagintaeva Z I, Kasenova S B, et al. Calorimetric Investigation of Heat Capacity of the ErMFe₂O_5.5(M = Mg, Ca, Sr, Ba) Ferrites in the Temperature Range of 298.15-673 K and Calculation of Their Thermodynamic Functions[J]. Published in Teplofizika Vysokikh Temperatur, 2015, 53(3): 358-362.

[9] Huang Z, Gao P, Zheng H, et al. Magnetic Enrichment Behavior of Monodispersed MFe₂O₄ Nanoferrites (M= Mg, Ca, Ni, Co, and Cu)[J]. Ceram. Int, 2019, 45(13): 15980-15989.

[10] Qin H, He Y Z, Xu P, et al. Spinel Ferrites (MFe₂O₄): Synthesis, Improvement and Catalytic Application in Environment and Energy Field[J]. Advances in Colloid and Interface Science, 2021, 294: 102 486.

[11] Thomas D, Erika A L, Oana C. Formation, Structure and Magnetic Properties of MFe₂O₄@SiO₂(M = Co, Mn, Zn, Ni, Cu) Nanocomposites[J]. Materials, 2021, 14(5): 1 139

[12] Tijerina-Rosa A, Greneche J M, Fuentes A F, et al. Partial Substitution of Cobalt by Rare-Earths (Gd or Sm) in Cobalt Ferrite: Effect on its Microstructure and Magnetic Properties[J]. Ceram. Int., 2019, 45(17): 22920-22929.

[13] Sagayaraj R, Aravazhi S, Chandrasekaran G. Effect of Zinc Content on Structural, Functional, Morphological, Resonance, Thermal and Magnetic Properties of Co_1−xZn_xFe₂O₄/PVP Nanocomposites[J]. J. Inorg. Organomet. Polym. Mater., 2019, 29: 2252-2261.

[14] King E G. Heat Capacities at Low Temperature and Entropies of Five Spinel Minerals[J]. The Journal of Physical chemistry, 1956, 60(4): 410-412.

[15] Schliesser J M, Huang B, Sahu S K, et al. Experimental Heat Capacities, Excess entropies, and Magnetic Properties of Bulk and Nano Fe₃O₄-Co₃O₄ and Fe₃O₄-Mn₃O₄ Spinel Solid Solutions[J]. J. Solid State Chem., 2018, 259: 79-90.

[16] Alzoubi G M, Alsmadi A M, Alna’washi G A, et al. Coexistence of Superparamagnetism and Spin-glass Like Behavior in Zinc-Substituted Cobalt Ferrite Nanoparticles[J]. Appl. Phys. A, 2020, 126: 1-11.

[17] Zhu J, Tong X, Niu S, et al. Effects of Magnetization on Thermoelectric Transport Properties of CoSb₃ Material[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2021, 36(3): 353-357.

[18] Martin A, Elvira F, Claudia I, et al. Role of Zn²⁺ Substitution on the Magnetic, Hyperthermic, and Relaxometric Properties of Cobalt Ferrite Nanoparticles[J]. J. Phys. Chem. C, 2019, 123(10): 6148-6157.

[19] Muscas G, Jovanovi S, Vukomanovic M, et al. Zn-doped Cobalt Ferrite: Tuning the Interactions by Chemical Composition[J]. J. Alloys Compd., 2019, 796: 203-209.

[20] Kumar D R, Ahmad S I, Lincoln C A, et al. Structural, Optical, Room-Temperature and Low-Temperature Magnetic Properties of Mg-Zn Nanoferrite Ceramics[J]. J. Asian Ceram. Soc., 2019, 7(1): 53-68.

[21] Ateia E E, Abdelmaksoud M K, Arman M M, et al. Comparative Study on the Physical Properties of Rare-Earth-Substituted Nano-Sized CoFe₂O₄[J]. Appl. Phys. A, 2020, 126(2): 91

[22] Dudnikov V A, Orlov Y S, Bushinsky M A, et al. Structural, Magnetic, Electronic, and Dilatation Properties of the Ordered Solid Solutions Ln_0.2Sr_0.8CoO_3−δ (Ln = Sm, Gd, Dy) with the Same Oxygen Nonstoichiometry Index δ[J]. J. Alloys Compd., 2020, 830: 154 629.

[23] Alberto P, Susana Y, Yolanda P, et al. Cubic Anisotropic Co- and Zn-Substituted Ferrite Nanoparticles as Multimodal Magnetic Agents[J]. ACS Appl. Mater Interfaces, 2020, 12(8): 9017-9031.

[24] Almessiere M A, Slimani Y, Trukhanov A V, et al. Strong Correlation Between Dy³⁺ Concentration, Structure, Magnetic and Microwave Properties of the [Ni_0.5Co_0.5](Dy_xFe_2−x)O₄ Nanosized Ferrites[J]. J. Ind. Eng. Chem., 2020, 90: 251-259.

[25] Yan M, Li C, Zou Y, et al. Synthesis and Characterization of Magnetic MAX Phase (Cr_2−xMn_x)GaC[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2020, 35: 363-367.

[26] Raut A V, Barkule R S, Shengule D R, et al. Synthesis, Structural Investigation and Magnetic Properties of Zn²⁺ Substituted Cobalt Ferrite Nanoparticles Prepared by Sol-Gel Auto-Combustion Technique[J]. J. Magn. Magn. Mater., 2014, 350: 87-92.

[27] Khozima H, Qassem I M, Mahdi L, et al. Structural and Magnetic Studies of Ga-doped Yttrium Iron Garnet[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2021, 36: 13-21.

[28] Thorat L M, Patil J Y, Nadargi D Y, et al. Co²⁺ Substituted Mg-Cu-Zn Ferrite: Evaluation of Structural, Magnetic, and Electromagnetic Properties[J]. J. Adv. Ceram., 2018, 7: 207-217.

[29] Abdel Maksoud M I A, El-Ghandour A, El-Sayyad G S, et al. Unveiling the Effect of Zn²⁺ Substitution in Enrichment of Structural, Magnetic, and Dielectric Properties of Cobalt Ferrite[J]. J. Inorg. Organomet. Polym. Mater., 2020, 30: 3709-3721.

[30] Nocikov V V. Debye-Einstein Model and Anomalies of Heat Capacity Temperature Dependences of Solid Solutions at Low Temperatures[J]. J. Therm. Anal. Calorim., 2019, 138(1): 265-272.

[31] Saroj L M. Heat Capacity and Magnetocaloric Effect in CoS_1.84Se_0.16[J]. J. Magn. Magn. Mater., 2019, 474: 619-623.

[32] Feng T, Li L, Shi Q, et al. Heat Capacity and Thermodynamic Functions of TiO₂(B) Nanowires[J]. J. Chem. Thermodyn, 2018, 119: 127-134.

[33] Suman K, Murli K M, Manoranjan K, et al. Magnetic Properties and Hyperthermia Action of Cobalt Zinc Ferrite Fibers[J]. J. Sol-Gel Sci. Technol., 2022, 101(3): 546-561.

[34] Sadovnikov S I, Gusev A I. Thermal Expansion, Heat Capacity and Phase Transformations in Nanocrystalline and Coarse-Crystalline Silver Sulfide at 290–970 K[J]. J. Therm. Anal. Calorim., 2018, 131: 1155-1164.

[35] Maxim I L, Evgeny V S, Charles A G, et al. A Calorimetric and Thermodynamic Investigation of Cs₆[(UO₂)₂(MoO₄)₃(MoO₅)] and Calculated Phase Behaviour in the System (Cs₂MoO₄ + UO₃ + H₂O)[J]. J. Chem. Thermodyn., 2021, 153: 106 274.

[36] Dai R, Zhang S H, Yin N, et al. Low-Temperature Heat Capacity and Standard Thermodynamic Functions of β-D-(-)-Arabinose (C₅H₁₀O₅)[J]. J. Chem. Thermodyn, 2016, 92: 60-65.

[37] Chen S P, Shi Q, Xia Z Q, et al. Magneto-Structural Correlation and Low Temperature Heat Capacity of a Mn(III) Quadridentate Schiffbase Coordination Compound[J]. J. Chem. Thermodyn, 2014, 74: 247-254.

[38] Drebushchak V A. Model-Free Temperature Scaling for Heat Capacity[J]. J. Therm. Anal. Calorim., 2017, 130: 5-13.

[39] Jurčišinová E, Jurčišin M. Influence of Metamagnetic Phase Transitions on Thermodynamics of Frustrated Systems with Octahedral Structure[J]. J. Magn. Magn. Mater., 2021, 524: 167 658.

[40] Lohaus S H, Johnson M B, Ahnn P F, et al. Thermodynamic Stability and Contributions to the Gibbs Free Energy of Nanocrystalline Ni₃Fe[J]. Phys. Rev. Materials, 2020, 4(8): 086002

[41] Chen S, Xia J, Dai J. Effects of Heating Processing on Microstructure and Magnetic Properties of Mn-Zn Ferrites Prepared via Chemical Co-Precipitation[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2015, 30(4): 684-688.

[42] Anna M S, Tatiana D M, Alexey V M, et al. Isobaric Heat Capacity and Standard Thermodynamic Properties of Cationordered Layered Perovskite-Like Oxides NaLnTiO₄ and A₂Ln₂Ti₃O₁₀ (A = H, Na, K; Ln = La, Nd, Gd)[J]. Thermochim. Acta., 2020, 686: 178 533.

[43] Wang G, Li Y, Gao Y, et al. Thermodynamic Study on Self-Propagating High Temperature Synthesis of TiB₂/Fe Composites[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2019, 34(4): 769-773.

[44] Prayoonsak P, Prutthipong T, Burapat I, et al. Structural, Thermodynamic, Electronic, and Magnetic Properties of Superconducting FeSe-CsCl Type: Ab Initio Searching Technique With Van Der Waals Corrections[J]. Mater. Chem. Phys., 2021, 267: 124 708.