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

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 Ni0.8Co0.2Fe2-x(Dy1-yTby)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 (Mr) increases from 0.06 to 0.17 µB/f.u. with the rare-earth (Dy and Tb) substitution and has achieved the maximum squareness ratio (Mr/Ms) = 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 dλ11dH = -0.764 nm/A whereas dλ12dH = 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.

Correlation between Cation Distribution and Magnetic and Dielectric Properties of Dy3+-Substituted Fe-Rich Cobalt Ferrite.

Designing electromagnetic materials, particularly those based on transition-metal-containing spinel ferrites, with a controlled structure, phase, and chemistry at the nanoscale dimensions while realizing enhanced electrical and magnetic properties continues to be a challenging problem. Herein, we report on the synthesis and structure-property correlation of dysprosium (Dy)-substituted iron-rich cobalt ferrite (Co0.8Fe2.2-xDyxO4; CFDO; x = 0.000-0.100) oxides with variable Dy3+ concentration. Chemical bonding analyses of CFDO nanomaterials using Raman spectroscopic analyses supported the spinel phase formation with high quality. Cation distribution determined from Mössbauer spectroscopy reveals the fact that Dy3+ occupies the octahedral site of the spinel lattice. Saturation magnetization (Ms) values calculated using Neel's two-sublattice model and cation distribution derived from Mossbauer's studies correlate well with the magnetization values obtained from SQUID measurements. The B-site hyperfine field decreases from 52.24 ± 0.10 to 49.26 ± 0.00 T, as evidenced by the Mössbauer spectra, with Dy substitution, which decreases the Fe-ion occupancy from the octahedral site of CFDO. Frequency-dependent dielectric constant indicates electron hopping in the grain interior, which ceases above 6.3 kHz. Dielectric measurements indicate that these CFDO compounds are useful for absorption at higher frequencies. Thus, using the combined approach based on Raman and Mössbauer spectroscopic analyses, the present work elucidates the structure, chemical bonding, and magnetic properties of Dy-substituted Fe-rich cobalt ferrite. CFDO may serve as a model system to apply to a class of Fe-rich ferromagnetic nanomaterials for electromagnetic and sensor applications.

Effect of Oleylamine on the Surface Chemistry, Morphology, Electronic Structure, and Magnetic Properties of Cobalt Ferrite Nanoparticles.

The influence of oleylamine (OLA) concentration on the crystallography, morphology, surface chemistry, chemical bonding, and magnetic properties of solvothermal synthesized CoFe2O4 (CFO) nanoparticles (NPs) has been thoroughly investigated. Varying OLA concentration (0.01-0.1 M) resulted in the formation of cubic spinel-structured CoFe2O4 NPs in the size-range of 20-14 (±1) nm. The Fourier transform spectroscopic analyses performed confirmed the OLA binding to the CFO NPs. The thermogravimetric measurements revealed monolayer and multilayer coating of OLA on CFO NPs, which were further supported by the small-angle X-ray scattering measurements. The magnetic measurements indicated that the maximum saturation (MS) and remanent (Mr) magnetization decreased with increasing OLA concentration. The ratio of maximum dipolar field (Hdip), coercivity (HC), and exchanged bias field (Hex) (at 10 K) to the average crystallite size (Dxrd), i.e., (Hdip/Dxrd), (HC/Dxrd), and (Hex/Dxrd), increased linearly with OLA concentration, indicating that OLA concurrently controls the particle size and interparticle interaction among the CFO NPs. The results and analyses demonstrate that the OLA-mediated synthesis allowed for modification of the structural and magnetic properties of CFO NPs, which could readily find potential application in electronics and biomedicine.

Eco-Friendly Synthesis, Crystal Chemistry, and Magnetic Properties of Manganese-Substituted CoFe2O4 Nanoparticles.

The authors report on the effect of manganese (Mn) substitution on the crystal chemistry, morphology, particle size distribution characteristics, chemical bonding, structure, and magnetic properties of cobalt ferrite (CoFe2O4) nanoparticles (NPs) synthesized by a simple, cost-effective, and eco-friendly one-pot aqueous hydrothermal method. Crystal structure analyses indicate that the Mn(II)-substituted cobalt ferrites, Co1-x Mn x Fe2O4 (CMFO, x = 0.0-0.5), were crystalline with a cubic inverse spinel structure (space group Fd 3 m ). The average crystallite size increases from 8 to 14 nm with increasing Mn(II) content; the crystal growth follows an exponential growth function while the lattice parameters follow Vegard's law. Chemical bonding analyses made using Raman spectroscopic studies further confirm the cubic inverse spinel phase. The relative changes in specific vibrational modes related to octahedral sites as a function of Mn content suggest a gradual change of measure of inversion of the ferrite lattice at nanoscale dimensions. Small-angle X-ray scattering and electron microscopy revealed a narrow particle size distribution with the spherical shape morphology of the CMFO NPs. The zero-field-cooled and field-cooled magnetic measurements revealed the superparamagnetic behavior of CMFO NPs at room temperature. The sample with x = 0.3 indicates a lower value of blocking temperature (9.16 K) with the improved (maximum) value of saturation magnetization. The results and the structure-composition-property correlation suggest that the economic, eco-friendly hydrothermal approach can be adopted to process superparamagnetic nanostructured magnetic materials at a relatively lower temperature for practical electronic and electromagnetic device applications.

Size and Chemistry Controlled Cobalt-Ferrite Nanoparticles and Their Anti-proliferative Effect against the MCF-7 Breast Cancer Cells.

Engineering cobalt ferrites for application in health and biomedical science poses a challenge in terms of nanoscale morphology with a controlled size, shape, and thermochemical stability coupled with controlled properties for biocompatibility. Here, we report a simple one-step, low temperature approach to produce crystalline, nanosized cobalt ferrites (CFO) with a size ∼4.7 nm and demonstrate their applicability in breast cancer treatment. Inherent physiochemical and magnetic properties, which are quite important for biomedical applications, along with cytotoxicity of CFO nanoparticles (NPs) are investigated in detail. X-ray diffraction analyses confirm the cubic spinel phase with the tensile strain in crystalline CFO NPs. Chemical bonding analyses using infrared and Raman spectroscopic studies also support the cubic spinel phase. Electron microscopy and small-angle X-ray scattering revealed the narrow particle-size distribution and spherical-shape morphology. The as-synthesized CFO NPs exhibit superparamagnetic character. Unsaturated magnetization behavior suggests the existence of disordered spins in the surface layers. The temperature dependence of the magnetic parameters, namely, saturation magnetization, coercivity, retentivity, and squareness ratio, also supports the surface-localized spins. Cytotoxic activity of the as-synthesized CFO NPs against the human breast cancer (MCF-7) cell line and normal human peripheral blood mononuclear cells (PBMC) has been evaluated. The mild response of CFO NPs in terms of their antiproliferative nature against cancer cells and negligible Cytotoxicity reflecting their human-safe-and-friendly nature makes them suitable for bioapplications. Moreover, assessment of toxicity toward human red blood cells (RBC) revealed (<3%) hemolysis as compared to the positive control, suggesting potential applications of CFO NPs for human cells.