Co1−xZnxFe2O4 nanoparticles (0 ≤ x ≤ 1) have been synthesized via a green sol–gel combustion method. The prepared samples were studied using X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), Raman, and magnetic measurements. All samples were found to be single phases and have a cubic Fd-3m structure. EDS analysis confirmed the presence of cobalt, zinc, iron, and oxygen in all studied samples. Raman spectra clearly show that Zn ions are preferentially located in T sites for low Zn concentrations. Due to their high crystallinity, the nanoparticles show high values of the magnetization, which increases with the Zn content for x < 0.5. The magnetic properties are discussed based on Raman results. Co ferrite doped with 30% of Zn produced the largest SAR values, which increase linearly from 148 to 840 W/gMNPs as the H is increased from 20 to 60 kA/m.
Co0.95R0.05Fe2O4 nanoparticles with R = La, Pr, Nd, Sm, and Eu were synthesized via an environmentally friendly sol–gel method. The prepared samples were studied using X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), X-ray photoelectron microscopy (XPS), and magnetic measurements. All compounds were found to be single phases adopting a cubic Fd-3m structure. EDS analysis confirmed the presence of Co, Fe, R, and oxygen in all cases. The XPS measurements reveal that the Co 2p core-level spectra are characteristic for Co3+ ions, as indicated by the 2p3/2 and 2p1/2 binding energies and spin–orbit splitting values. The analysis of the Fe 2p core-level spectra reveals the presence of both Fe3+ and Fe2+ ions in the investigated samples. The doped samples exhibit lower saturation magnetizations than the pristine sample. Very good agreement with the saturation magnetization values was obtained if we assumed that the light rare-earth ions occupy octahedral sites and their magnetic moments align parallel to those of the 3d transition metal ions. The ZFC-FC curves indicate that some nanoparticles remain superparamagnetic, while others exhibit ferrimagnetic ordering at room temperature, suggesting the presence of interparticle interactions. The Mr/Ms ratio at room temperature reflects the dominance of magnetostatic interactions.
Here we report investigations of bulk and nano-sized Pr0.65Sr(0.35−x)CaxMnO3 compounds (x ≤ 0.3). Solid-state reaction was implemented for polycrystalline compounds and a modified sol–gel method was used for nanocrystalline compounds. X-ray diffraction disclosed diminishing cell volume with increasing Ca substitution in Pbnm space group for all samples. Optical microscopy was used for bulk surface morphology and transmission electron microscopy was utilized for nano-sized samples. Iodometric titration showed oxygen deficiency for bulk compounds and oxygen excess for nano-sized particles. Measurements of resistivity of bulk samples revealed features at temperatures associated with grain boundary condition and with ferromagnetic (FM)/paramagnetic (PM) transition. All samples exhibited negative magnetoresistivity. Magnetic critical behavior analysis suggested the polycrystalline samples are governed by a tricritical mean field model while nanocrystalline samples are governed by a mean field model. Curie temperatures values lower with increasing Ca substitution from 295 K for the parent compound to 201 K for x = 0.2. Bulk compounds exhibit high entropy change, with the highest value of 9.21 J/kgK for x = 0.2. Magnetocaloric effect and the possibility of tuning the Curie temperature by Ca substitution of Sr make the investigated bulk polycrystalline compounds promising for application in magnetic refrigeration. Nano-sized samples possess wider effective entropy change temperature (ΔTfwhm) and lower entropy changes of around 4 J/kgK which, however, puts in doubt their straightforward potential for applications as magnetocaloric materials.
We report the successful synthesis and a complete magnetic characterization of CoFe2O4@SiO2@Au magnetoplasmonic nanoparticles. The CoFe2O4 magnetic nanoparticles were prepared using the hydrothermal method. A subsequent SiO2 shell followed by a plasmonic Au shell were deposited on the magnetic core creating magnetoplasmonic nanoparticles with a core–shell architecture. A spin-glass-type magnetism was shown at the surface of the CoFe2O4 nanograins. Depending on the external magnetic field, two types of spin-glass were identified and analyzed in correlation with the exchange field acting on octahedral and tetrahedral iron sites. The magnetization per formula unit of the CoFe2O4 core is not changed in the case of CoFe2O4@SiO2@Au nanocomposites. The gold nanoparticles creating the plasmonic shell show a giant diamagnetic susceptibility, dependent on their crystallite sizes.
Co1−xMnxFe2O4 nanoparticles (0 ≤ x ≤ 1) have been prepared via the hydrothermal method. The prepared samples were studied using X-ray diffraction measurements (XRD), transmission electron microscopy (TEM), Raman spectroscopy, and magnetic measurements. All studied samples were found to be single phases and to have a cubic Fd-3m structure. The average crystalline sizes are between 7.8 and 15 nm. EDS analysis confirmed the presence of cobalt, manganese, iron, and oxygen in all prepared samples. It was found by Raman spectroscopy that Fe3+ would be placed on octahedral sites while Fe2+ would, in turn, be displaced to tetrahedral sites while Mn ions will be placed on both sites. Both Mn2+ and Mn4+ are present in studied ferrites. The experimental saturation magnetizations for doped samples are much higher when compared with previous reports, reaching values between 3.71 and 6.7 μB/f.u. The doping with Mn in nanocrystalline cobalt ferrite enhanced the magnetic properties due to changes in the cation distribution between the two sublattices. The higher magnetic moments are explained by the presence of Mn4+ ions located preferentially on tetrahedral sites while Mn2+ prefer octahedral sites, and by the high quality and crystallinity of our samples the nanoparticles being almost monodomain. Large values of the coercive field were found at 4.2 K while the hysteresis is almost absent in all investigated samples at room temperature.
Co0.95R0.05Fe2O4 nanoparticles were synthesized using a sol-gel approach incorporating bio-based agents and were found to be single phases adopting a cubic Fd-3m structure. XPS shows the presence of Gd3+ and Ho3+ ions. The spin–orbit splitting of about 15.4 eV observed in Co 2p core-level spectra is an indication that Co is predominantly present as Co3+ state, while the satellite structures located at about 6 eV higher energies than the main lines confirm the existence of divalent Co in Co0.95R0.05Fe2O4. The positions of the Co 3s and Fe 3s main peaks obtained by curve fitting and the exchange splitting obtained values for Co 3s and Fe 3s levels point to the high Co3+/Co2+ and Fe3+/Fe2+ ratios in both samples. The saturation magnetizations are smaller for the doped samples compared to the pristine ones. For theoretical magnetization calculation, we have considered that the heavy rare earths are in octahedral sites and their magnetic moments are aligned antiparallelly with 3d transition magnetic moments. ZFC-FC curves shows that some nanoparticles remain superparamagnetic, while the rest are ferrimagnetic, ordered at room temperature, and showing interparticle interactions. The MS/Ms ratio at room temperature is below 0.5, indicating the predominance of magnetostatic interactions.