S. S. Starchikov

Magnetic and Mössbauer spectroscopy studies of hollow microcapsules made of silica-coated CoFe 2 O 4 nanoparticles

The hollow microcapsules made of silica-coated CoFe2O4 nanoparticles were synthesized using chemical co-precipitation, followed by the sol–gel method. Poly(MMA-co-MAA) microspheres were used as a core template which can be completely removed after annealing at 450 °C. The microcapsules are monodisperse with the outer diameter of about 450 nm and the thickness of the shell is about 50 nm. The nanoparticles of Co-ferrite are single crystalline. The size of the nanoparticles and magnetic properties of CoFe2O4/SiO2 hollow spheres can be tuned with high accuracy at the annealing stage. The Mossbauer data indicate that CoFe2O4 ferrite is an inverse spinel, in which Fe3+ and Co2+ ions are distributed in both octahedral and tetrahedral sites with the inversion degree close to the bulk ferrite value. At low temperature the CoFe2O4/SiO2 nanoparticles are in antiferromagnetic (AFM) state due to the canted or triangular magnetic structure. Under heating in the applied field, AFM structure transforms to the ferrimagnetic (FM) structure, that increases the magnetization. The Mossbauer data revealed that the small size CoFe2O4/SiO2 particles do not show superparamagnetic behavior, but they transit to the paramagnetic state by the jump-like first order magnetic transition (JMT). This effect is a specific property of the magnetic nanoparticles isolated by inert material. The suggested method of synthesis can be modified with various bio-ligands on the silane surface, and such materials can find many applications in diagnostics and bio-separation.

Structural, Magnetic, and Electronic Properties of Mixed Spinel NiFe2–xCrxO4 Nanoparticles Synthesized by Chemical Combustion

A series of nickel-chromium-ferrite NiFe2-xCrxO4 (with x = 1.25) nanoparticles (NPs) with a cubic spinel structure and with size d ranging from 1.6 to 47.7 nm was synthesized by the solution combustion method. A dual structure of all phonon modes revealed in Raman spectra is associated with metal cations of different types present in the spinel lattice sites. Mössbauer spectra of small NPs exhibit superparamagnetic behavior. However, the transition into the paramagnetic state occurs at a temperature that is unusually high for small particles (TN is about 240 K in the d = 4.5 nm NPs). The larger NPs with d > 20 nm do not exhibit superparamagnetic properties up to the Neel temperature. From the magnetic and Mössbauer data, the cation occupation of the tetrahedral (A) and octahedral [B] sites was determined (Fe0.75Ni0.25)[Ni0.75Cr1.25]O4. The saturation magnetization MS in the largest NPs is about (0.98-0.95) μB, which is more than twice higher the value in bulk ferrite (Fe)[CrNi]O4. At low temperatures the total magnetic moment of the ferrite coincides with the direction of the B-sublattice moment. In the NPs with d > 20 nm, the compensation of the magnetic moments of A- and B-sublattices was revealed at about Tcom = 360-365 K. This value significantly exceeds the point Tcom in bulk ferrites NiFexCr2-xO4 (about 315 K) with the similar Cr concentration. However, in the smaller NPs NiFe0.75Cr1.25O4 with d ≤ 11.7 nm, the compensation effect does not occur. The magnetic anomalies are explained in terms of highly frustrated magnetic ordering in the B sublattice, which appears due to the competition of AFM and FM exchange interactions and results in a canted magnetic structure.