Effect of Dy3+ and Tb3+ Rare-Earth Cation Co-Substitution on the Structure, Magnetic, and Magnetostrictive Properties of Ni-Co-Ferrites

Swati K Gaikwad; Shahaji P Kharat; Keerthi Haritha; Yesh D Kolekar; C V Ramana

doi:10.1021/acs.inorgchem.3c01117

Effect of Dy³⁺ and Tb³⁺ Rare-Earth Cation Co-Substitution on the Structure, Magnetic, and Magnetostrictive Properties of Ni-Co-Ferrites

Inorg Chem. 2023 Jul 31;62(30):11837-11848. doi: 10.1021/acs.inorgchem.3c01117. Epub 2023 Jul 14.

Authors

Swati K Gaikwad^{1

2}, Shahaji P Kharat^{1

2}, Keerthi Haritha³, Yesh D Kolekar¹, C V Ramana^{4

5}

Affiliations

¹ Department of Physics, Savitribai Phule Pune University, Pune 411007, Maharashtra, India.
² Department of Physics, Fergusson College (Autonomous), Pune 411004, Maharashtra, India.
³ Environmental Science and Engineering, University of Texas at El Paso, 500 W. University Ave., El Paso, Texas 79968, United States.
⁴ Centre for Advanced Materials Research (CMR), University of Texas at El Paso, El Paso, Texas 79968, United States.
⁵ Department of Aerospace & Mechanical Engineering, University of Texas at El Paso, El Paso, Texas 79968, United States.

PMID: 37450403
DOI: 10.1021/acs.inorgchem.3c01117

Abstract

The design and development of electromagnetic and magnetoelectric materials with enhanced properties and performance are desirable for numerous technologies, which are based on integrated electromagnetic materials and components. Nevertheless, engineering the crystalline materials with multi-complex chemistry and multiple cations is challenging. In this context, herein, we report on the effect of rare-earth (RE) cations, namely, Dy³⁺ and Tb³⁺, co-substituted into the Co-Ni-mixed ferrite materials for applications in stress/torque sensors. The RE-cations that co-substituted Co-Ni-ferrite materials with a composition of Ni_0.8Co_0.2Fe_2-x(Dy_1-yTb_y)_xO₄ (x = 0-0.1, y = 0.3; NCFDT) were prepared by the high-temperature solid-state chemical reaction method. The effect of variable composition (x) on the structure, morphology, chemical bonding, and magnetic properties of NCFDT materials is investigated in detail, and the structure-property optimization enabled realizing magnetostrictive NCFDT for sensor applications. X-ray diffraction analysis coupled with Rietveld refinement confirms the face-centered cubic crystal structure. Chemical bonding analysis made using Raman spectroscopic and Fourier transform infrared spectroscopic measurements validates the active modes corresponding to the spinel ferrite structure. The effect of Dy³⁺ and Tb³⁺ substitution is primarily seen in the grain size (range of 5-15 μm), as evident from the scanning electron microscopy patterns. Energy-dispersive spectroscopy confirms the presence of all constituent elements with expected composition and without any impurities. The magnetic property measurements indicate that the remnant magnetization (M_r) increases from 0.06 to 0.17 μ_B/f.u. with the rare-earth (Dy and Tb) substitution and has achieved the maximum squareness ratio (M_r/M_s) = 0.097 at x = 0.10. To validate their application potential in magneto-mechanical sensors, we have measured the magnetostriction coefficients (λ₁₁ and λ₁₂), which demonstrate high values of λ₁₁ = -92 ppm (along the parallel direction) and λ₁₂ = 66 ppm (along the perpendicular direction) for NCFDT with x = 0.05 at H = 7000 Oe. In addition, the maximum value of strain sensitivity is observed, particularly $\frac{{dλ}_{11}}{d H}$ = -0.764 nm/A whereas $\frac{{dλ}_{12}}{d H}$ = 0.361 nm/A. The correlation between strain sensitivity (dλ/dH) and susceptibility (dM/dH), as derived from magnetostriction and magnetization measurements, respectively, is established. The outcomes of this study indicate that Ni-Co-ferrites with Dy³⁺ and Tb³⁺ substitution are suitable for stress/torque sensors. These NCFDT ferrites may also be useful as a necessary constitutive phase for the manufacture of magnetoelectric composite materials, making them appropriate for magnetic field sensors and energy harvesting applications.