The evolution of the electronic structure and magnetic properties with Co substitution for Fe in the solid solution Fe1−xCoxGa3 was studied by means of electrical resistivity, magnetization, ab initio band structure calculations, and nuclear spin-lattice relaxation 1/T1 of the 69,71 Ga nuclei. Temperature dependencies of the electrical resistivity reveal that the evolution from the semiconducting to the metallic state in the Fe1−xCoxGa3 system occurs at 0.025 < x < 0.075. The 69,71 (1/T1) was studied as a function of temperature in a wide temperature range of 2−300 K for the concentrations x = 0.0, 0.5, and 1.0. In the parent semiconducting compound FeGa3, the temperature dependence of the 69 (1/T1) exhibits a huge maximum at about T ∼ 6 K indicating the existence of in-gap states. The opposite binary compound, CoGa3, demonstrates a metallic Korringa behavior with 1/T1 ∝ T . In Fe0.5Co0.5Ga3, the relaxation is strongly enhanced due to spin fluctuations and follows 1/T1 ∝ T 1/2 , which is a unique feature of weakly and nearly antiferromagnetic metals. This itinerant antiferromagnetic behavior contrasts with both magnetization measurements, showing localized magnetism with a relatively low effective moment of about 0.7 µB/f.u., and ab initio band structure calculations, where a ferromagnetic state with an ordered moment of 0.5 µB/f.u. is predicted. The results are discussed in terms of the interplay between the localized and itinerant magnetism including in-gap states and spin fluctuations.

The hollow microcapsules made of silica-coated CoFe 2 O 4 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 CoFe 2 O 4 /SiO 2 hollow spheres can be tuned with high accuracy at the annealing stage. The Mössbauer data indicate that CoFe 2 O 4 ferrite is an inverse spinel, in which Fe 3+ and Co 2+ ions are distributed in both octahedral and tetrahedral sites with the inversion degree close to the bulk ferrite value. At low temperature the CoFe 2 O 4 /SiO 2 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 Mössbauer data revealed that the small size CoFe 2 O 4 /SiO 2 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.

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A series of nickel-chromium-ferrite NiFeCrO (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 (T 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 (FeNi)[NiCr]O. The saturation magnetization M in the largest NPs is about (0.98-0.95) μ, which is more than twice higher the value in bulk ferrite (Fe)[CrNi]O. 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 T = 360-365 K. This value significantly exceeds the point T in bulk ferrites NiFeCrO (about 315 K) with the similar Cr concentration. However, in the smaller NPs NiFeCrO 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.